Method of forming antifouling coating film

ABSTRACT

Provided is a method of forming an antifouling coating film including the steps of [1] preparing a colored antifouling paint containing a prescribed Si-containing hydrolyzable resin and a color pigment such that a coating film having a target dry film thickness T completely hides a surface of an object to be coated, the colored antifouling paint has a color difference ΔE1 between the coating film having the thickness T and a coating film having a dry film thickness of 0.8 T, at least 2.0, and preferably the colored antifouling paint has a color difference ΔE2 between the coating film having the thickness T and a coating film having a dry film thickness of 1.2 T, less than 1, and [2] coating a surface of the object with the colored antifouling paint until the surface of the object is completely hidden by the coating film formed from the colored antifouling paint.

TECHNICAL FIELD

The present invention relates to a method of forming an antifoulingcoating film on an object to be coated such as marine vessels and powergenerating plants, and more specifically to a method of substantiallyuniformly forming an antifouling coating film having a prescribed dryfilm thickness in a simplified manner.

BACKGROUND ART

A surface of such an underwater structure as marine vessels and powergenerating plants is painted with an antifouling paint in order toprevent adhesion of such aquatic organisms as acorn barnacle, mussels,and algae. Since the underwater structures painted with the antifoulingpaint are normally large in size, painting with an antifouling paint isoften carried out by using a crane truck or the like. It is not easy,however, to paint the entire surface of an underwater structure having alarge area uniformly to a prescribed film thickness.

An antifouling paint has a prescribed dry coating film thickness range(in particular, a minimum coating film thickness) necessary forexhibiting expected coating film performance (such as antifoulingperformance). For example, when a thickness is smaller than theprescribed minimum coating film thickness and even though a portionwhere a film thickness is insufficient is a part of the entire surface,expected antifouling performance cannot be provided to an underwaterstructure and an effective antifouling period is virtually shortened.

In order to address such a problem, for example, Japanese PatentLaying-Open No. 2000-005692 (PTL 1) discloses a method of forming anantifouling coating film by using such a film thickness determinableantifouling paint characterized in that a color difference between thefilm thickness determinable antifouling paint and an object to becoated, a color difference between a completely hiding coating film witha target dry film thickness and a coating film having a dry filmthickness less than (target dry film thickness−50) μm, and a colordifference between the completely hiding coating film with the targetdry film thickness and a coating film having a dry film thicknessexceeding (target dry film thickness+50) μm are each within a prescribedrange and that a content of an antifouling agent and a color pigment isnot greater than a prescribed value. According to such a film thicknessdeterminable antifouling paint, whether the coating film has reached aprescribed film thickness or not can be determined by visually observingchange in color difference between the coating film being applied andthe object to be coated, and hence painting with the antifouling paintcan be carried out substantially uniformly in a simplified manner,without excess or shortage in coating film thickness.

The film thickness determinable antifouling paint described in PTL 1above, however, is relatively small in color difference between thecoating film having the target dry film thickness and the coating filmimmediately before reaching the target dry film thickness, and thereforeit may sometimes be difficult to determine whether a coating film beingapplied has reached a prescribed film thickness or not by visualobservation by a paint operator, and there has been a room forimprovement.

CITATION LIST Patent Literature

-   PTL 1: Japanese Patent Laying-Open No. 2000-005692

SUMMARY OF INVENTION Technical Problem

The present invention was made to solve the above-described problem, andan object thereof is to provide a method allowing extremely easydetermination as to whether a coating film being applied has reached aprescribed film thickness or not and thus allowing a uniform antifoulingcoating film having a prescribed dry film thickness to be formed moreaccurately in a more simplified manner.

Solution to Problem

The present invention is directed to a method of forming an antifoulingcoating film on a surface of an object to be coated, and characterizedby including the steps [1] and [2] below:

[1] preparing a colored antifouling paint containing a hydrolyzableresin and a color pigment and satisfying such conditions that

-   -   (a) a coating film formed from the colored antifouling paint        having a target dry film thickness T completely hides the        surface of the object to be coated,    -   (b) a color difference ΔE1 between the coating film formed from        the colored antifouling paint having the target dry film        thickness T and a coating film formed from the colored        antifouling paint having a dry film thickness of 0.8 T is equal        to or greater than 2.0, and    -   (c) the hydrolyzable resin above contains a hydrolyzable        resin (i) and/or a hydrolyzable resin (ii); and

[2] coating the surface of the object to be coated with the coloredantifouling paint until the surface of the object to be coated iscompletely hidden by the coating film formed from the coloredantifouling paint.

Here, hydrolyzable resin (i) above is a hydrolyzable resin having ametal-atom-containing group containing a divalent metal atom M and atleast one type of a silicon-containing group selected from the groupconsisting of

a group expressed in a general formula (I)

[where a and b each independently represent an integer from 2 to 5, mrepresents an integer from 0 to 50, n represents an integer from 3 to80, and R¹ to R⁵ each independently represent an alkyl group, an alkoxygroup, a phenyl group, a substituted phenyl group, a phenoxy group, or asubstituted phenoxy group],

a group expressed in a general formula (II)

[where c and d each independently represent an integer from 2 to 5, prepresents an integer from 0 to 50, and R⁶, R⁷, and R⁸ eachindependently represent an alkyl group, R^(a), or R^(b), with R^(a)being

-   -   (where x represents an integer from 0 to 20 and R²³ to R²⁷ are        identical or different and represent an alkyl group), with R^(b)        being

-   -   (where y represents an integer from 1 to 20 and R²⁸ and R²⁹ are        identical or different and represent an alkyl group)],

a group expressed in a general formula (III)

[where e, f, g, and h each independently represent an integer from 2 to5, q and s each independently represent an integer from 0 to 50, rrepresents an integer from 3 to 80, and R⁹ to R¹² each independentlyrepresent an alkyl group, an alkoxy group, a phenyl group, a substitutedphenyl group, a phenoxy group, or a substituted phenoxy group], and

a group expressed in a general formula (IV)

[where i, j, k, and l each independently represent an integer from 2 to5, t and u each independently represent an integer from 0 to 50, v and weach independently represent an integer from 0 to 20, and R¹³ to R²² areidentical or different and represent an alkyl group].

In addition, hydrolyzable resin (ii) above is a hydrolyzable resinhaving at least one type of a silicon-containing group selected from thegroup consisting of the groups expressed in the general formulae (I),(II), (III), and (IV) above and a triorganosilyloxy carbonyl groupexpressed in a general formula (V)

[where R⁴⁰, R⁴¹, and R⁴² are identical or different and represent ahydrocarbon residue having a carbon number from 1 to 20].

Color difference ΔE1 above is preferably not smaller than 2.5. Inaddition, the colored antifouling paint above preferably satisfies sucha condition (d) that a color difference ΔE2 between the coating filmformed from the colored antifouling paint having the target dry filmthickness T and a coating film formed from the colored antifouling painthaving a dry film thickness of 1.2 T is less than 1. Color differenceΔE2 is more preferably not greater than 0.5.

In the method of forming an antifouling coating film according to thepresent invention, preferably, whether the surface of the object to becoated has completely been hidden or not is determined based on visualobservation.

A content of the hydrolyzable resin above is preferably from 30 to 97mass % in a paint solid content.

The metal-atom-containing group which hydrolyzable resin (i) above hasis preferably at least one type of group selected from the groupconsisting of groups expressed in general formulae (VI) and (VII) below.

Here, in the general formula (VI) above, M represents a divalent metalatom and R³⁰ represents an organic acid residue or an alcohol residue.

Here, in the general formula (VII) above, M represents a divalent metalatom.

Hydrolyzable resin (i) above is preferably a resin including aconstitutional unit derived from at least one type of asilicon-containing polymerizable monomer (a) selected from the groupconsisting of a monomer (a1) expressed in a general formula (I′) below,a monomer (a2) expressed in a general formula (In below, a monomer (a3)expressed in a general formula (III′) below, and a monomer (a4)expressed in a general formula (IV′) below and a constitutional unitderived from a metal-atom-containing polymerizable monomer (b)containing a divalent metal atom M.

Here, in the general formula (I′) above, R³¹ represents a hydrogen atomor a methyl group, and a, b, m, n, and R¹ to R⁵ represent the samemeaning as described above.

Here, in general formula (II′) above, R³² represents a hydrogen atom ora methyl group, and c, d, p, and R⁶ to R⁸ represent the same meaning asdescribed above.

Here, in the general formula (III′) above, R³³ and R³⁴ represent ahydrogen atom or a methyl group, and e, f, g, h, q, r, s, and R⁹ to R¹²represent the same meaning as described above.

Here, in the general formula (IV′) above, R³⁵ and R³⁶ represent ahydrogen atom or a methyl group, and i, j, k, l, t, u, v, w, and R¹³ toR²² represent the same meaning as described above.

Metal-atom-containing polymerizable monomer (b) containing divalentmetal atom M above preferably includes at least one type selected fromthe group consisting of a monomer (b1) expressed in a general formula(VI′) below and a monomer (b2) expressed in a general formula (VII′)below.

Here, in the general formula (VI′) above, R³⁷ represents a hydrogen atomor a methyl group and M and R³⁰ represent the same meaning as describedabove.

Here, in the general formula (VII′) above, R³⁸ and R³⁹ represent ahydrogen atom or a methyl group and M represents the same meaning asdescribed above.

Hydrolyzable resin (ii) above preferably further has at least one typeof a metal-atom-containing group selected from the group consisting ofgroups expressed in the general formulae (VI) and (VII) above.

Hydrolyzable resin (ii) above is preferably a resin including aconstitutional unit derived from at least one type of asilicon-containing polymerizable monomer (a) selected from the groupconsisting of a monomer (a1) expressed in the general formula (I′)above, a monomer (a2) expressed in the general formula (II′) above, amonomer (a3) expressed in the general formula (III′) above, and amonomer (a4) expressed in the general formula (IV′) above and aconstitutional unit derived from triorganosilyl (meth)acrylate (c)expressed in a general formula (V′) below.

Here, in the general formula (V′) above, R⁴³ represents a hydrogen atomor a methyl group and R⁴⁰ to R⁴² represent the same meaning as describedabove.

Hydrolyzable resin (ii) above preferably further includes aconstitutional unit derived from at least one type of ametal-atom-containing polymerizable monomer (b) selected from the groupconsisting of a monomer (b1) expressed in the general formula (VI′)above and a monomer (b2) expressed in the general formula (VII′) above.

The colored antifouling paint can further contain an antifouling agent.In this case, a content of the antifouling agent is preferably equal toor lower than 10 mass in a paint solid content.

In addition, the colored antifouling paint above can further contain athermoplastic resin and/or a plasticizer. In this case, a total contentof the thermoplastic resin and the plasticizer is preferably 3 to 100parts by mass with respect to 100 parts by mass of the hydrolyzableresin above.

The thermoplastic resin above is preferably at least one type selectedfrom the group consisting of chlorinated paraffin, polyvinyl ether,rosin, and a vinyl chloride-isobutyl vinyl ether copolymer.

In addition, the plasticizer above is preferably at least one typeselected from the group consisting of a phthalate-ester-basedplasticizer and a phosphoric-ester-based plasticizer.

The colored antifouling paint above can also be prepared by mixing twoor more types of antifouling paints different from one another incontent of the color pigment, although satisfying the conditions (a) to(c) above.

The object to be coated above which is coated with the coloredantifouling paint may have an undercoat coating film formed from ananti-corrosive paint or an antifouling paint on its surface. In thiscase, a surface of the undercoat coating film is coated with the coloredantifouling paint. The object to be coated can be a structure made ofsteel, plastic, or concrete, and in particular it can be an underwaterstructure.

Advantageous Effects of Invention

The present invention provides a colored antifouling paint having a filmthickness determination function, of which color difference between acoating film having a target dry film thickness and a coating filmimmediately before reaching the target dry film thickness is greaterthan that of a conventional paint. According to the method of thepresent invention using the colored antifouling paint, whether a coatingfilm being applied has reached a prescribed film thickness or not canreadily be determined, and a uniform antifouling coating film having aprescribed dry film thickness can accurately be formed. Thus, adhesionor the like of aquatic organisms due to an insufficient film thicknessthat has often conventionally occurred can be prevented. In addition,since an excessive film thickness can also be prevented, a paint canalso be saved. Moreover, according to the method of the presentinvention, an antifouling coating film excellent in a long-termantifouling property and resistance to cracking can be formed.

Further, according to the method of the present invention, since such acomplicated operation as successively measuring a coating film thicknessand checking whether the coating film has reached a prescribed filmthickness or not can be avoided, significant improvement in efficiencyin a painting operation can be achieved, and burden imposed on a paintoperator can considerably be lessened.

The method according to the present invention can be applied toantifouling painting of various structures (in particular, underwaterstructures). According to the method of the present invention, in such acase as providing an outer surface of such a large-sized structure as amarine vessel with antifouling painting, a uniform antifouling coatingfilm having a prescribed dry film thickness can accurately be formed ina simplified manner even on a structure or on a part thereof which isdifficult to paint.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram showing relation of a color difference ΔE between atopcoat antifouling coating film having each dry film thickness and atopcoat antifouling coating film having a target dry film thickness inpaints 3 to 15 prepared in Examples and Comparative Examples.

FIG. 2 is a diagram showing a part of FIG. 1 (in the vicinity of atarget dry film thickness of 125 μm) in an enlarged view.

DESCRIPTION OF EMBODIMENTS

The present invention will be described hereinafter in detail.

<Colored Antifouling Paint>

In a method of forming an antifouling coating film according to thepresent invention, a colored antifouling paint containing a prescribedhydrolyzable resin and a color pigment is employed as a paint forforming an antifouling coating film. As will be described in detaillater, this colored antifouling paint is an antifouling paint having a“film thickness determination function” for allowing determination as towhether a prescribed film thickness has been reached or not, byobserving change in color difference between a coating film beingapplied and a surface of an object to be coated.

A colored antifouling paint employed in the present invention will bedescribed hereinafter in detail.

(A) Hydrolyzable Resin

A colored antifouling paint contains hydrolyzable resin (i) orhydrolyzable resin (ii) or both of them as a vehicle component.Hydrolyzable resins (i) and (ii) are excellent in resin transparency anda sharp color tone of a color pigment is not interfered by a color toneof the resin. Therefore, various sharp color tones in accordance with ahue of a color pigment can be provided to an antifouling paint. Thus, acolor difference between the colored antifouling paint and the surfaceof the object to be coated can be increased and dependence of a colortone of a coating film on a film thickness, inter alia, dependence of acolor tone of a coating film on a film thickness from immediately beforetarget dry film thickness T (around 0.8 T) to target dry film thicknessT can be made greater, and thus an excellent film thicknessdetermination function is provided to the colored antifouling paint. Inaddition, since various sharp color tones can be provided to theantifouling paint (there can be color variation of an antifoulingpaint), a degree of freedom in colors of the surface of the object to becoated, to which the method according to the present invention can beapplied, increases, and the method of the present invention issubstantially applicable whichever color the surface of the object to becoated may have.

Moreover, since hydrolyzable resins (i) and (ii) themselves have goodantifouling performance based on their own hydrolyzability and asilicon-containing group, a colored antifouling paint containinghydrolyzable resin(s) (i) and/or (ii) can form an antifouling coatingfilm exhibiting high antifouling performance for a long period in astable manner (having an excellent long-term antifouling property) eventhough a separate antifouling agent is not contained or an amount ofblend thereof is small. Being free from a separate antifouling agent ordecrease in an amount of blend thereof means that a sharp color tone ofa color pigment is less likely to be interfered by an antifouling agent,which can further improve sharpness, color variation, and a filmthickness determination function of a colored antifouling paint.

[Hydrolyzable Resin (i)]

Hydrolyzable resin (i) that can be contained in the colored antifoulingpaint has at least one silicon-containing group selected from the groupconsisting of groups expressed in the general formulae (I), (II), (III),and (IV) above and at least one metal-atom-containing group containingdivalent metal atom M. Such hydrolyzable resin (i) having a specificsilicon-containing group and a metal-atom-containing group exhibits sucha property as being gradually hydrolyzed in water (in particular in seawater), owing to a hydrolyzability of the metal-atom-containing group.Therefore, an antifouling coating film formed from a colored antifoulingpaint containing hydrolyzable resin (i) as a vehicle has its surfaceself-polished by being immersed in water, and thus renewability of thesurface of the coating film is obtained. Therefore, an organism is lesslikely to adhere, and together with an antifouling effect as a result ofhydrolysis of the metal-atom-containing group and an antifouling effectexhibited by the silicon-containing group, excellent antifoulingperformance is exhibited until the coating film is completely consumedeven in a case of not containing an antifouling agent.

In the general formula (I) above, a and b each independently representan integer from 2 to 5, m represents an integer from 0 to 50, and nrepresents an integer from 3 to 80. R¹ to R⁵ each independentlyrepresent an alkyl group, an alkoxy group, a phenyl group, a substitutedphenyl group, a phenoxy group, or a substituted phenoxy group.

In the general formula (II) above, c and d each independently representan integer from 2 to 5 and p represents an integer from 0 to 50. R⁶, R⁷,and R⁸ each independently represent an alkyl group, R^(a), or R^(b).R^(a) and R^(b) are as described above.

In the general formula (III) above, e, f, g, and h each independentlyrepresent an integer from 2 to 5, q and s each independently representan integer from 0 to 50, and r represents an integer from 3 to 80. R⁹ toR¹² each independently represent an alkyl group, an alkoxy group, aphenyl group, a substituted phenyl group, a phenoxy group, or asubstituted phenoxy group.

In addition, in the general formula (IV) above, i, j, k, and l eachindependently represent an integer from 2 to 5, t and u eachindependently represent an integer from 0 to 50, and v and w eachindependently represent an integer from 0 to 20. R¹³ to R²² areidentical or different and represent an alkyl group.

Hydrolyzable resin (i) may have two or more types of silicon-containinggroups selected from the group consisting of the groups expressed in thegeneral formulae (I), (II), (III), and (IV) above. In this case,hydrolyzable resin (i) may have two or more types of the groupsexpressed in the general formula (I) above, two or more types of thegroups expressed in the general formula (II) above, two or more types ofthe groups expressed in the general formula (III) above, and/or two ormore types of the groups expressed in the general formula (IV) above.

The metal-atom-containing group containing divalent metal atom M whichhydrolyzable resin (i) has is preferably at least one type of groupselected from the group consisting of the groups expressed in thegeneral formulae (VI) and (VII) above. This is because it can maintain aself-polishing property of the coating film for a long period in astable manner, and thus it can form a coating film excellent in along-term antifouling property and also in resistance to cracking andadhesiveness to an underlying substrate. In the general formulae (VI)and (VII) above, M represents a divalent metal atom and R³⁰ representsan organic acid residue or an alcohol residue. Hydrolyzable resin (i)may have both of the groups expressed in the general formulae (VI) and(VII) above. Examples of divalent metal atom M include Mg, Zn, Cu, andthe like, and preferably Zn or Cu is employed.

Hydrolyzable resin (i) is not particularly limited so long as it has thesilicon-containing group and the metal-atom-containing group above,however, an acrylic resin including a constitutional unit derived fromat least one type of silicon-containing polymerizable monomer (a)selected from the group consisting of monomer (a1) expressed in thegeneral formula (I′) above, monomer (a2) expressed in the generalformulae (II′) above, monomer (a3) expressed in the general formula(III′) above, and monomer (a4) expressed in the general formula (IV′)above and a constitutional unit derived from metal-atom-containingpolymerizable monomer (b) containing divalent metal atom M can suitablybe employed.

Here, in the general formula (I′) above, R³¹ represents a hydrogen atomor a methyl group, and a, b, m, n, and R¹ to R⁵ represent the samemeaning as described above. In the general formula (II′) above, R³²represents a hydrogen atom or a methyl group, and c, d, p, and R⁶ to R⁸represent the same meaning as described above. In the general formula(III′) above, R³³ and R³⁴ represent a hydrogen atom or a methyl group,and e, f, g, h, q, r, s, and R⁹ to R¹² represent the same meaning asdescribed above. In the general formula (IV′) above, R³⁵ and R³⁶represent a hydrogen atom or a methyl group, and i, j, k, l, t, u, v, w,and R¹³ to R²² represent the same meaning as described above.

Monomer (a1) expressed in the general formula (I′) above, monomer (a2)expressed in the general formula (II′), monomer (a3) expressed in thegeneral formula (III′), and monomer (a4) expressed in the generalformula (IV′) are silicon-containing polymerizable monomers having thesilicon-containing groups expressed in the general formulae (I), (II),(III), and (IV) above, respectively.

The metal-atom-containing polymerizable monomer (b) containing divalentmetal atom M above preferably contains at least one type selected fromthe group consisting of monomer (b1) expressed in the general formula(VI′) above and monomer (b2) expressed in (VII′). This is because it canmaintain a self-polishing property of the coating film for a long periodin a stable manner, and thus it can form a coating film excellent in along-term antifouling property and also in resistance to cracking andadhesiveness to an underlying substrate. In the general formula (VI′)above, R³⁷ represents a hydrogen atom or a methyl group and M and R³⁰represent the same meaning as described above. In addition, in thegeneral formula (VII′) above, R³⁸ and R³⁹ represent a hydrogen atom or amethyl group and M represents the same meaning as described above.

Monomer (b1) expressed in the general formula (VI′) above and monomer(b2) expressed in (VII′) above are metal-atom-containing polymerizablemonomers having the metal-atom-containing groups expressed in thegeneral formulae (VI) and (VII) above, respectively.

[1] Silicon-Containing Polymerizable Monomer (a)

Silicon-containing polymerizable monomer (a1) which can formhydrolyzable resin (i) is expressed in the general formula (I′) above,where a and b each independently represent an integer from 2 to 5, mrepresents an integer from 0 to 50, and n represents an integer from 3to 80. R¹ to R⁵ each independently represent an alkyl group, an alkoxygroup, a phenyl group, a substituted phenyl group, a phenoxy group, or asubstituted phenoxy group, and R³¹ represents a hydrogen atom or amethyl group. By employing silicon-containing polymerizable monomer (a1)as silicon-containing polymerizable monomer (a), hydrolyzable resin (i)which is an acrylic resin having the silicon-containing group expressedin the general formula (I) above in a side chain is obtained.

Here, m in the general formula (I′) above (the general formula (I) abovebeing also similar, to be understood similarly hereafter), whichrepresents an average degree of polymerization of a polyether structuremay be set to 0, however, it is preferably greater than 0 becauserecoatability on an old coating film tends to be good. In addition,preferably, m is not greater than 50 because water resistance of thecoating film tends to be good and m is not greater than 30 becauserecoatability on an old coating film tends to be good. More preferably,m is within a range from 3 to 25 and further preferably within a rangefrom 5 to 20.

Here, a in the general formula (I′) above is preferably set to 2 or 3,and a monomer with a being set to 2 and a monomer with a being set to 3may both be employed. Here, b is preferably set to 2 or 3.

Here, n in the general formula (I′) above represents an average degreeof polymerization of a silicon-containing structure, and it representsan integer in a range from 3 to 80. By setting n to 3 or greater, afurther enhanced antifouling effect can be exhibited. In addition, bysetting n to 80 or smaller, good compatibility with other polymerizablemonomers is exhibited and solubility of obtained hydrolyzable resin (i)in a general organic solvent can be improved. Preferably, n is within arange from 5 to 50 and more preferably within a range from 8 to 40.

In the general formula (I′) above, R¹ to R⁵ are preferably an alkylgroup having a carbon number from 1 to 18, more preferably a methylgroup or an ethyl group, and further preferably a methyl group.

Specific examples of silicon-containing polymerizable monomer (a1)expressed in the general formula (I′) above include, as a monomer with mbeing set to 0, “FM-0711”, “FM-0721”, and “FM-0725” (each of which is atrade name) manufactured by Chisso Corporation, “X-24-8201”,“X-22-174DX”, and “X-22-2426” (each of which is a trade name)manufactured by Shin-Etsu Chemical Co., Ltd., and the like. In addition,examples of a monomer with m being greater than 0 include “F2-254-04”and “F2-254-14) (each of which is a trade name) manufactured by NipponUnicar Co., Ltd., and the like. Though products manufactured by NipponUnicar Co., Ltd. are shown with their trade names as specific examplesof silicon-containing polymerizable monomer (a1), silicone business thathad been operated by Nippon Unicar Co., Ltd. was assigned to Dow CorningToray Co., Ltd. in 2004 and corresponding products are currentlyavailable from the assignee. This is also the case with productsmanufactured by Nippon Unicar Co., Ltd. shown below.

Hydrolyzable resin (i) may include constitutional units derived from twoor more types of silicon-containing polymerizable monomers (a1) assilicon-containing polymerizable monomer (a).

Silicon-containing polymerizable monomer (a2) which can formhydrolyzable resin (i) is expressed in the general formula (II′) above,where c and d each independently represent an integer from 2 to 5 and prepresents an integer from 0 to 50. R⁶, R⁷, and R⁸ each independentlyrepresent an alkyl group, R^(a), or R^(b), and R³² represents a hydrogenatom or a methyl group. R^(a) and R^(b) are as described above. Byemploying silicon-containing polymerizable monomer (a2) assilicon-containing polymerizable monomer (a), hydrolyzable resin (i)which is an acrylic resin having the silicon-containing group expressedin the general formula (II) above in a side chain is obtained.

Here, p in the general formula (II′) above (the general formula (II)above being also similar, to be understood similarly hereafter), whichrepresents an average degree of polymerization of a polyether structuremay be set to 0, however, it is preferably greater than 0 becauserecoatability on an old coating film tends to be good. In addition,preferably, p is not greater than 50 because water resistance of thecoating film tends to be good and p is not greater than 30 becauserecoatability on an old coating film tends to be good. More preferably,p is within a range from 3 to 25 and further preferably within a rangefrom 5 to 20. Here, c in the general formula (II′) above is preferablyset to 2 or 3, and a monomer with c being set to 2 and a monomer with cbeing set to 3 may both be employed. Here, d is preferably set to 2 or3.

Here, x and y in the general formula (II′) above represent an averagedegree of polymerization of a silicon-containing structure or apolyether structure introduced in a side chain, and they represent aninteger in a range from 0 to 20 and an integer in a range from 1 to 20,respectively. By setting x and y not greater than 20, good compatibilitywith other polymerizable monomers is exhibited and solubility ofobtained hydrolyzable resin (i) in a general organic solvent can beimproved. Preferably, x and y are within a range not greater than 10 andmore preferably within a range not greater than 5.

Examples of an alkyl group that can be selected for R⁶ to R⁸ and R²³ toR²⁹ in the general formula (II′) above include a methyl group, an ethylgroup, an n-propyl group, an n-butyl group, and the like. A methyl groupor an ethyl group is preferred and a methyl group is more preferred.

Specific examples of silicon-containing polymerizable monomer (a2)expressed in the general formula (II′) above include, as a monomer withp being set to 0, “TM-0701” (a trade name) manufactured by ChissoCorporation, “X-22-2404” (a trade name) manufactured by Shin-EtsuChemical Co., Ltd., “F2-250-01” and “F2-302-01” (a trade name)manufactured by Nippon Unicar Co., Ltd., and the like. In addition,examples of a monomer with p being greater than 0 include “F2-302-04”(each of which above is a trade name) manufactured by Nippon Unicar Co.,Ltd., and the like.

Hydrolyzable resin (i) may include constitutional units derived from twoor more types of silicon-containing polymerizable monomers (a2) assilicon-containing polymerizable monomer (a).

Silicon-containing polymerizable monomer (a3) which can formhydrolyzable resin (i) is expressed in the general formula (III′) above,where e, f, g, and h each independently represent an integer from 2 to5, q and s each independently represent an integer from 0 to 50, and rrepresents an integer from 3 to 80. R⁹ to R¹² each independentlyrepresent an alkyl group, an alkoxy group, a phenyl group, a substitutedphenyl group, a phenoxy group, or a substituted phenoxy group, and R³³and R³⁴ represent a hydrogen atom or a methyl group. By employingsilicon-containing polymerizable monomer (a3) as silicon-containingpolymerizable monomer (a), hydrolyzable resin (i) which is an acrylicresin having the silicon-containing group expressed in the generalformula (III) above (this silicon-containing group being a cross-linkinggroup cross-linking polymer main chains) is obtained.

Here, q and s in the general formula (III′) above (the general formula(III) above being also similar, to be understood similarly hereafter),both of which represent an average degree of polymerization of apolyether structure may be set to 0, however, they are preferablygreater than 0 because recoatability on an old coating film tends to begood. In addition, preferably, q and s are not greater than 50 becausewater resistance of the coating film tends to be good and q and s arenot greater than 30 because recoatability on an old coating film tendsto be good. More preferably, q and are within a range from 3 to 25 andfurther preferably within a range from 5 to 20.

Here, e and h in the general formula (III′) above are preferably set to2 or 3, and a monomer with e and h being set to 2 and a monomer with eand h being set to 3 may both be employed. Here, f and g are preferablyset to 2 or 3.

Here, r in the general formula (III′) above represents an average degreeof polymerization of a silicon-containing structure and it represents aninteger in a range from 3 to 80. By setting r not smaller than 3, afurther enhanced antifouling effect can be expressed. By setting r notgreater than 80, good compatibility with other polymerizable monomers isexhibited and solubility of obtained hydrolyzable resin (i) in a generalorganic solvent can be improved. Preferably, r is within a range from 5to 50 and more preferably within a range from 8 to 40.

In the general formula (III′) above, R⁹ to R¹² are preferably an alkylgroup having a carbon number from 1 to 18, more preferably a methylgroup or an ethyl group, and further preferably a methyl group.

Specific examples of silicon-containing polymerizable monomer (a3)expressed in the general formula (III′) above include, as a monomer withq and s being set to 0, “FM-7711”, “FM-7721”, and “FM-7725” (each ofwhich is a trade name) manufactured by Chisso Corporation, “F2-311-02”(a trade name) manufactured by Nippon Unicar Co., Ltd., and the like. Inaddition, examples of a monomer with q and s being greater than 0include “F2-354-04” (a trade name) manufactured by Nippon Unicar Co.,Ltd., and the like.

Hydrolyzable resin (i) may include constitutional units derived from twoor more types of silicon-containing polymerizable monomers (a3) assilicon-containing polymerizable monomer (a).

Silicon-containing polymerizable monomer (a4) which can formhydrolyzable resin (i) is expressed in the general formula (IV′) above,where i, j, k, and l each independently represent an integer from 2 to5, t and u each independently represent an integer from 0 to 50, and vand w each independently represent an integer from 0 to 20. R¹³ to R²²are identical or different and represent an alkyl group, and R³⁵ and R³⁶represent a hydrogen atom or a methyl group. By employingsilicon-containing polymerizable monomer (a4) as silicon-containingpolymerizable monomer (a), hydrolyzable resin (i) which is an acrylicresin having the silicon-containing group expressed in the generalformula (IV) above (this silicon-containing group being a cross-linkinggroup cross-linking polymer main chains) is obtained.

Here, t and u in the general formula (IV′) above (the general formula(IV) above being also similar, to be understood similarly hereafter),both of which represent an average degree of polymerization of apolyether structure may be set to 0, however, they are preferablygreater than 0 because recoatability on an old coating film tends to begood. In addition, preferably, t and u are not greater than 50 becausewater resistance of the coating film tends to be good and t and u arenot greater than 30 because recoatability on an old coating film tendsto be good. More preferably, t and u are within a range from 3 to 25 andfurther preferably within a range from 5 to 20.

Here, i and l in the general formula (IV′) above are preferably set to 2or 3, and a monomer with i and l being 2 and a monomer with i and lbeing 3 may both be employed. Here, j and k are preferably set to 2 or3.

Here, v and w in the general formula (IV′) above represent an averagedegree of polymerization of a silicon-containing structure introduced ina side chain, and they represent an integer in a range from 0 to 20. Bysetting v and w not greater than 20, good compatibility with otherpolymerizable monomers is exhibited and solubility of obtainedhydrolyzable resin (i) in a general organic solvent can be improved.Preferably, v and w are within a range not greater than 10 and morepreferably within a range not greater than 5.

Examples of an alkyl group that can be selected for R¹³ to R²² in thegeneral formula (IV′) above include a methyl group, an ethyl group, ann-propyl group, an n-butyl group, and the like. A methyl group or anethyl group is preferred and a methyl group is more preferred.

Specific examples of silicon-containing polymerizable monomer (a4)expressed in the general formula (IV′) above include, as a monomer witht and u being set to 0, “F2-312-01” (a trade name) manufactured byNippon Unicar Co., Ltd., and the like. In addition, examples of amonomer with t and u being greater than 0 include “F2-312-04” (a tradename) manufactured by Nippon Unicar Co., Ltd., and the like.

Hydrolyzable resin (i) may include constitutional units derived from twoor more types of silicon-containing polymerizable monomers (a4) assilicon-containing polymerizable monomer (a).

In addition, hydrolyzable resin (i) may include constitutional unitsderived from two or more types of silicon-containing polymerizablemonomers selected from silicon-containing polymerizable monomers (a1),(a2), (a3), and (a4). Among these, an embodiment in which amono-terminal (meth)acrylic modified silicon-containing polymerizablemonomer [silicon-containing polymerizable monomer(s) (a1) and/or (a2)]and a both-terminal (meth)acrylic modified silicon-containingpolymerizable monomer [silicon-containing polymerizable monomer(s) (a3)and/or (a4)] are both used can be exemplified as one of preferredembodiments.

In all the constitutional units forming hydrolyzable resin (i), acontent of the constitutional unit derived from silicon-containingpolymerizable monomer (a) is preferably 1 to 60 mass %, more preferably5 to 50 mass %, and further preferably 10 to 40 mass %. By setting thecontent to 1 mass % or higher, an antifouling effect tends to beexhibited also in a case where an antifouling agent is not containedseparately, and by setting the content to 60 mass % or lower, along-term antifouling property and adhesiveness with an underlyingsubstrate tend to be in good balance.

[2] Metal-Atom-Containing Polymerizable Monomer (b)

Metal-atom-containing polymerizable monomer (b) is a monomer used forintroducing a metal-atom-containing group containing divalent metal atomM into hydrolyzable resin (i). In a case not containing ametal-atom-containing group, hydrolyzability of an obtained resin isinsufficient, which results in failure in obtaining a goodself-polishing property of the coating film. It is thus difficult toobtain a coating film exhibiting a high antifouling property. Inaddition, in a case not containing a metal-atom-containing group,adhesiveness with an underlying substrate of a coating film andresistance to cracking tend to be poor. Examples of divalent metal atomM include Mg, Zn, Cu, and the like, and Zn or Cu is preferably employed.

Metal-atom-containing polymerizable monomer (b1) which can formhydrolyzable resin (i) is expressed in the general formula (VI′) above,where R³⁷ represents a hydrogen atom or a methyl group, M represents adivalent metal atom, and R³⁰ represents an organic acid residue or analcohol residue. By employing metal-atom-containing polymerizablemonomer (b1) as metal-atom-containing polymerizable monomer (b),hydrolyzable resin (i) which is an acrylic resin having themetal-atom-containing group expressed in the general formula (VI) aboveis obtained.

Examples of an organic acid forming an organic acid residue in R³⁰include such monobasic organic acids as acetic acid, monochloroaceticacid, monofluoroacetic acid, propionic acid, caproic acid, caprylicacid, 2-ethylhexanoic acid, capric acid, versatic acid, isostearic acid,palmitic acid, cresotic acid, oleic acid, elaidic acid, linoleic acid,linolenic acid, stearolic acid, ricinoleic acid, ricinoelaidic acid,brassidic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoicacid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid,quinoline carboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, and pyrubic acid. Among these, use of an acid having anorganic acid residue of an aliphatic acid type tends to allow a coatingfilm free from cracks or peel-off to be maintained for a long period,which is preferred. In particular, zinc oleate (meth)acrylate or zincversatate (meth)acrylate having high plasticity is preferably employedas metal-atom-containing polymerizable monomer (b1).

In addition, monobasic cyclic organic acids other than aromatic organicacids can be exemplified as other preferred organic acids. As amonobasic cyclic organic acid, for example, not only an organic acidhaving a cycloalkyl group such as naphthenic acid but also a resin acidsuch as a tricyclic resin acid, a salt thereof, and the like can beexemplified. As a tricyclic resin acid, for example, a monobasic acidhaving a diterpene-based hydrocarbon skeleton and the like can beexemplified, and examples thereof include a compound having an abietane,pimarane, isopimarane, or labdane skeleton. More specifically, examplesinclude abietic acid, neoabietic acid, dehydroabietic acid, hydrogenatedabietic acid, palustric acid, pimaric acid, isopimaric acid, levopimaricacid, dextropimaric acid, sandaracopimaric acid, and a salt thereof, andthe like. Among these, abietic acid, hydrogenated abietic acid, and asalt thereof are preferred, because hydrolysis moderately occurs, whichleads to an excellent long-term antifouling property and also excellentresistance to cracking of a coating film and availability.

The monobasic cyclic organic acid above does not have to highly bepurified, and for example, turpentine, a resin acid of a pine, or thelike can also be employed. Examples thereof can include rosin,hydrogenated rosin, disproportionated rosin, and the like, as well asnaphthenic acid. The rosin herein refers to gum rosin, wood rosin, talloil rosin, and the like. The rosin, the hydrogenated rosin, and thedisproportionated rosin are preferred because they are inexpensive andreadily available and excellent in handleability, and they exhibit along-term antifouling property.

An acid value of the monobasic cyclic organic acid above is preferablynot less than 100 mgKOH/g and not more than 220 mgKOH/g, more preferablynot less than 120 mgKOH/g and not more than 190 mgKOH/g, and furtherpreferably not less than 140 mgKOH/g and not more than 185 mgKOH/g. Useof a monobasic cyclic organic acid having an acid value within the rangeabove as the monobasic cyclic organic acid forming R³⁰ will bring abouta moderate rate of hydrolysis of hydrolyzable resin (i), andconsequently a self-polishing property of the coating film can bemaintained in a stable manner for a long period and hence an antifoulingeffect can be maintained for a longer period.

An organic acid residue of metal-atom-containing polymerizable monomer(b1) may be formed only of a single type of organic acid or two or moretypes of organic acids.

As a method of producing metal-atom-containing polymerizable monomer(b1) having an organic acid residue as R³⁰, for example, a method ofcausing reaction among an inorganic metal compound, acarboxyl-group-containing radical polymerizable monomer such as a(meth)acrylic acid, and a non-polymerizable organic acid (an organicacid forming the organic acid residue above) in an organic solventcontaining an alcohol-based compound can be exemplified. In addition, aconstitutional unit derived from metal-atom-containing polymerizablemonomer (b1) can be formed also with a method of causing reaction amonga resin obtained by polymerization of a monomer mixture including acarboxyl-group-containing radical polymerizable monomer such as a(meth)acrylic acid, a metal compound, and a non-polymerizable organicacid (an organic acid forming the organic acid residue above).

Metal-atom-containing polymerizable monomer (b2) which can formhydrolyzable resin (i) is expressed in the general formula (VIP) above,where R³⁸ and R³⁹ represent a hydrogen atom or a methyl group and Mrepresents a divalent metal atom. By employing metal-atom-containingpolymerizable monomer (b2) as metal-atom-containing polymerizablemonomer (b), hydrolyzable resin (i) which is an acrylic resin having themetal-atom-containing group expressed in the general formula (VII) above(this metal-atom-containing group being a cross-linking groupcross-linking polymer main chains) is obtained.

Specific examples of metal-atom-containing polymerizable monomer (b2)include magnesium acrylate [(CH₂═CHCOO)₂Mg], magnesium methacrylate[(CH₂═C(CH₃)COO)₂Mg], zinc acrylate [(CH₂═CHCOO)₂Zn], zinc methacrylate[(CH₂═C(CH₃)COO)₂Zn], copper acrylate [(CH₂═CHCOO)₂Cu], coppermethacrylate [(CH₂═C(CH₃)COO)₂Cu], and the like. One type or two or moretypes of these can be selected and used as appropriate.

As a method of producing metal-atom-containing polymerizable monomer(b2), for example, a method of causing reaction between a polymerizableunsaturated organic acid such as a (meth)acrylic acid and a metalcompound in an organic solvent containing an alcohol-based compound, inthe presence of water, can be exemplified. In this case, a content ofwater in a reactant is preferably adjusted within a range from 0.01 to30 mass %.

Hydrolyzable resin (i) may include both of a constitutional unit derivedfrom metal-atom-containing polymerizable monomer (b1) and aconstitutional unit derived from metal-atom-containing polymerizablemonomer (b2). In a case where metal-atom-containing polymerizablemonomer (b1) and metal-atom-containing polymerizable monomer (b2) areboth used as monomers forming hydrolyzable resin (i), a ratio of contentin hydrolyzable resin (i) between the constitutional unit derived frommetal-atom-containing polymerizable monomer (b1) and the constitutionalunit derived from metal-atom-containing polymerizable monomer (b2) ispreferably in a range from 20/80 to 80/20 (a molar ratio) and morepreferably in a range from 30/70 to 70/30 (a molar ratio). By adjustingthe ratio of content within this range, even in a case where anantifouling agent is not contained or an amount of blend thereof issmall, an antifouling coating film exhibiting a high antifoulingproperty for a long period and excellent also in resistance to crackingand adhesiveness with an underlying substrate tends to be obtained.

In all the constitutional units forming hydrolyzable resin (i), acontent of the constitutional unit derived from metal-atom-containingpolymerizable monomer (b) is preferably 5 to 30 mass % and morepreferably 10 to 20 mass %. By setting the content to 5 mass % orhigher, adhesiveness with an underlying substrate tends to be improvedand a self-polishing property of a formed coating film tends to bemaintained in a stable manner for a long period. By setting the contentto 30 mass % or lower, an effect to improve balance between a long-termself-polishing property and resistance to cracking and adhesiveness withan underlying substrate after immersion in seawater tend to benoticeable, and a long-term self-polishing property tends to bemaintained and coating film properties tend to be improved.

In hydrolyzable resin (i), a ratio of a content between theconstitutional unit derived from silicon-containing polymerizablemonomer (a) and the constitutional unit derived frommetal-atom-containing polymerizable monomer (b) is within a range in amass ratio preferably from 30/70 to 90/10 and more preferably from 45/55to 85/15. By setting the ratio to 30/70 or higher, an antifouling effecttends to be exhibited even in a case where an antifouling agent is notcontained separately. In a case where the ratio is lower than 30/70,flexibility of an obtained coating film may be impaired or aself-polishing property of the coating film may be too high. Further, bysetting the ratio to 90/10 or lower, a long-term antifouling propertyand adhesiveness with an underlying substrate tends to be in goodbalance. In a case where the ratio exceeds 90/10, hydrolysis of anobtained coating film may be impaired and hence a self-polishingproperty of the coating film may be impaired.

[3] Other Monomer Components (d)

Hydrolyzable resin (i) may contain a constitutional unit derived from amonomer component (d) other than silicon-containing polymerizablemonomer (a) and metal-atom-containing polymerizable monomer (b) above.

Other monomer components (d) are not particularly limited so long asthey are unsaturated monomers that can be copolymerized withsilicon-containing polymerizable monomer (a) and metal-atom-containingpolymerizable monomer (b) above, and examples thereof include: a(meth)acrylic ester monomer such as methyl (meth)acrylate,ethyl(meth)acrylate, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate,2-(2-ethylhexaoxy)ethyl(meth)acrylate,1-methyl-2-methoxyethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate,3-methyl-3-methoxybutyl(meth)acrylate, m-methoxyphenyl(meth)acrylate,p-methoxyphenyl (meth)acrylate, o-methoxyphenylethyl(meth)acrylate,m-methoxyphenylethyl (meth)acrylate, p-methoxyphenylethyl(meth)acrylate,n-propyl(meth)acrylate, i-propyl (meth)acrylate, n-butyl(meth)acrylate,i-butyl(meth)acrylate, t-butyl(meth)acrylate,2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate,benzyl (meth)acrylate, phenyl(meth)acrylate, isobornyl(meth)acrylate,cyclohexyl (meth)acrylate, and glycidyl(meth)acrylate; ahydroxyl-group-containing monomer such as 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate,2-hydroxybutyl(meth)acrylate, and 4-hydroxybutyl (meth)acrylate; anadduct of 2-hydroxyethyl(meth)acrylate with ethylene oxide, propyleneoxide, γ-butyrolactone, ε-caprolactone, or the like; a dimer or a trimerof 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, or thelike; a monomer having a plurality of hydroxyl groups such as glycerol(meth)acrylate; a primary or secondary amino group containing vinylmonomer such as butylaminoethyl (meth)acrylate and (meth)acrylamide; atertiary amino group containing vinyl monomer such asdimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate,dimethylaminopropyl(meth)acrylate, dimethylaminobutyl(meth)acrylate,dibutylaminoethyl(meth)acrylate, dimethylaminoethyl(meth)acrylamide, anddimethylaminopropyl(meth)acrylamide; a heterocyclic basic monomer suchas vinylpyrrolidone, vinylpyridine, and vinylcarbazole; and avinyl-based monomer such as styrene, vinyltoluene, α-methyl styrene,(meth)acrylonitrile, vinyl acetate, and vinyl propionate.

In all the constitutional units forming hydrolyzable resin (i), acontent of the constitutional unit derived from other monomer components(d) above is preferably 0.1 to 89 mass %, more preferably 7 to 75 mass%, and further preferably 10 to 70 mass %. By setting the content to 0.1mass % or higher, various characteristics of an obtained antifoulingpaint composition can be in good balance. By setting the content to 89mass % or lower, good long-term hydrolyzability is provided to a formedcoating film, an excellent antifouling property can be exhibited even ina case where an antifouling agent is not used, and balance thereof withadhesiveness of the coating film to an underlying substrate tends to begood.

Though a method of producing hydrolyzable resin (i) above is notparticularly limited, the hydrolyzable resin can be produced, forexample, by causing a monomer mixture in which the monomers above aremixed to react for 5 to 14 hours at a reaction temperature from 60 to180° C. in the presence of a radical initiator. Examples of a radicalinitiator include 2,2-azobisisobutyronitrile,2,2-azobis(2,4-dimethylvaleronitrile),2,2-azobis(2-methylbutyronitrile), benzoyl peroxide, cumenehydroperoxide, lauryl peroxide, di-t-butylperoxide,t-butylperoxy-2-ethylhexanoate, and the like. Not only solutionpolymerization performed in an organic solvent but also emulsionpolymerization, suspension polymerization, or the like can be adopted asa polymerization method, however, solution polymerization using such ageneral organic solvent as toluene, xylene, methyl isobutyl ketone, andn-butyl acetate is advantageous from a point of view of productivity andperformance of hydrolyzable resin (i).

In a case where metal-atom-containing polymerizable monomer (b2) isused, a chain transfer agent is preferably used in order to achieve ahigh-solid antifouling paint, improved productivity, and suppressedgeneration of cullet during polymerization. From a point of view ofcompatibility with metal-atom-containing polymerizable monomer (b), achain transfer agent other than mercaptan is preferred as a chaintransfer agent, and a styrene dimer or the like is preferred.

Although being different depending on a polymerization condition, aweight-average molecular weight of hydrolyzable resin (i) is normallywithin a range from 1000 to 3000000, more preferably within a range from3000 to 100000, and further preferably within a range from 5000 to50000. When a weight-average molecular weight is equal to or more than1000, an antifouling property tends to be exhibited when a coating filmis formed. When a weight-average molecular weight is equal to or lessthan 3000000, hydrolyzable resin (i) tends to uniformly be dispersed ina paint composition. It is noted that a weight-average molecular weightherein refers to a weight-average molecular weight in terms ofpolystyrene measured with gel permeation chromatography (GPC).

The fact that hydrolyzable resin (i) is a resin containing one or moretypes of silicon-containing groups expressed in the general formulae (I)to (IV) above (or the fact that it is a resin containing aconstitutional unit derived from one or more types of silicon-containingpolymerizable monomers (a1) to (a4)) can be confirmed, for example, byusing ¹H-NMR, ICP emission spectroscopy, or the like. The fact thathydrolyzable resin (i) is a resin containing one or more types ofmetal-atom-containing groups expressed in the general formulae (VI) to(VII) above (the fact that it is a resin containing a constitutionalunit derived from one or more types of metal-atom-containingpolymerizable monomers (b1) to (b2)) can be confirmed, for example, withatomic absorption spectroscopy or the like.

[Hydrolyzable Resin (ii)]

Hydrolyzable resin (ii) that can be contained in a colored antifoulingpaint has at least one type of silicon-containing group selected fromthe group consisting of the groups expressed in the general formulae(I), (II), (III), and (IV) above and the triorganosilyloxy carbonylgroup expressed in the general formula (V) above. Hydrolyzable resin(ii) having such a specific silicon-containing group and atriorganosilyloxy carbonyl group shows such a property that it isgradually hydrolyzed in water (in particular, in seawater) due tohydrolyzability of a triorganosilyloxy carbonyl group. Therefore, anantifouling coating film formed from a colored antifouling paintcontaining hydrolyzable resin (ii) as a vehicle has its surfaceself-polished by being immersed in water and thus renewability of thesurface of the coating film is obtained. Therefore, an organism is lesslikely to adhere and the antifouling coating film exhibits excellentantifouling performance until it is completely consumed even in a caseof not containing an antifouling agent, together with an antifoulingeffect as a result of hydrolysis of a triorganosilyloxy carbonyl groupand an antifouling effect exhibited by the silicon-containing group.Further, the antifouling coating film formed from the coloredantifouling paint containing hydrolyzable resin (ii) is excellent inresistance to cracking.

Details of the silicon-containing groups expressed in the generalformulae (I), (II), (III), and (IV) above are as described in connectionwith hydrolyzable resin (i).

In the general formula (V) above, R⁴⁰, R⁴¹, and R⁴² are identical ordifferent and represent a hydrocarbon residue having a carbon numberfrom 1 to 20. Hydrolyzable resin (ii) may have two or more types oftriorganosilyloxy carbonyl groups expressed in the general formula (V)above. Specific examples of a hydrocarbon residue having a carbon numberfrom 1 to 20 include a linear-chain or branched alkyl group having acarbon number not more than 20 such as a methyl group, an ethyl group,an n-propyl group, an isopropyl group, an n-butyl group, an isobutylgroup, a sec-butyl group, a tert-butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anundecyl group, a dodecyl group, a tridecyl group, and a tetradecylgroup, a cyclic alkyl group such as a cyclohexyl group and a substitutedcyclohexyl group, an aryl group, a substituted aryl group, and the like.Examples of the substituted aryl group include an aryl group substitutedwith halogen, an alkyl group having a carbon number up to around 18, anacyl group, a nitro group, an amino group, or the like, and the like.Among these, since a coating film exhibiting a stable polishing rate(polishing speed) can be obtained and antifouling performance can bemaintained in a stable manner for a long period, the triorganosilyloxycarbonyl group expressed in the general formula (V) above preferablyincludes an isopropyl group as a hydrocarbon residue, and morepreferably each of R⁴⁰, R⁴¹ and R⁴² is an isopropyl group.

In addition, since a coating film of which self-polishing property canbe maintained in a stable manner for a long period, which is thusexcellent in long-term antifouling property and excellent in resistanceto cracking and adhesiveness with an underlying substrate, tends to beformed, hydrolyzable resin (ii) preferably further has at least one typeof a metal-atom-containing group selected from the group consisting ofthe groups expressed in the general formulae (VI) and (VII) above. Inthe general formulae (VI) and (VII) above, M represents a divalent metalatom and R³⁰ represents an organic acid residue or an alcohol residue.Hydrolyzable resin (ii) may have both of the general formulae (VI) and(VII) above. Examples of divalent metal atom M include Mg, Zn, Cu, andthe like, and preferably Zn or Cu is employed.

Though hydrolyzable resin (ii) above is not particularly limited so longas it has the silicon-containing group and the triorganosilyloxycarbonyl group above, an acrylic resin including a constitutional unitderived from at least one type of silicon-containing polymerizablemonomer (a) selected from the group consisting of monomer (a1) expressedin the general formula (I′) above, monomer (a2) expressed in the generalformula (II′) above, monomer (a3) expressed in the general formula(III′) above, and monomer (a4) expressed in the general formula (IV′)above and a constitutional unit derived fromtriorganosilyl(meth)acrylate (c) expressed in the general formula (V′)above can suitably be employed. Details of monomers (a1) to (a4) are asdescribed in connection with hydrolyzable resin (i),Triorganosilyl(meth)acrylate (c) expressed in the general formula (V′)above is a polymerizable monomer having the triorganosilyloxy carbonylgroup expressed in the general formula (V) above.

Triorganosilyl(meth)acrylate (c) expressed in the general formula (V′)above is a monomer used for introducing the triorganosilyloxy carbonylgroup expressed in the general formula (V) above into hydrolyzable resin(ii). As the triorganosilyloxy carbonyl group is introduced in additionto the silicon-containing group above, a good self-polishing property ofa coating film can be obtained and a coating film excellent in long-termantifouling property can be obtained. R⁴⁰, R⁴¹, and R⁴² in the generalformula (V′) above represent the same meaning as R⁴⁰, R⁴¹, and R⁴² inthe general formula (V) above.

In all the constitutional units forming hydrolyzable resin (ii), a totalcontent of the constitutional units derived from silicon-containingpolymerizable monomer (a) above and triorganosilyl(meth)acrylate (c) ispreferably 5 to 90 mass % and more preferably 15 to 80 mass %. Bysetting the content to 5 mass % or higher, good hydrolyzability of theresin tends to be ensured, and by setting the content to 90 mass % orlower, sufficient hardness of a coating film tends to be ensured.

In addition, a ratio of a content in hydrolyzable resin (ii) between theconstitutional unit derived from silicon-containing polymerizablemonomer (a) above and the constitutional unit derived fromtriorganosilyl(meth)acrylate (b) is preferably within a range from 20/80to 80/20 (a mass ratio) and more preferably within a range from 30/70 to70/30 (a mass ratio).

Since a self-polishing property of a coating film can be maintained in astable manner for a long period and the coating film further excellentin long-term antifouling property and excellent in resistance tocracking and adhesiveness with an underlying substrate thus tends to beformed, hydrolyzable resin (ii) preferably further includes aconstitutional unit derived from at least one type ofmetal-atom-containing polymerizable monomer (b) selected from the groupconsisting of monomer (b1) expressed in the general formula (VI′) aboveand monomer (b2) expressed in (VII′). Monomer (b1) expressed in thegeneral formula (VP) above and monomer (b2) expressed in (VII′) aremetal-atom-containing polymerizable monomers having themetal-atom-containing groups expressed in the general formulae (VI) and(VII) above, respectively. Details of monomers (b1) and (b2) are asdescribed in connection with hydrolyzable resin (i),

Hydrolyzable resin (ii) may include both of the constitutional unitderived from metal-atom-containing polymerizable monomer (b1) and theconstitutional unit derived from metal-atom-containing polymerizablemonomer (b2).

In all the constitutional units forming hydrolyzable resin (ii), acontent of the constitutional unit derived from metal-atom-containingpolymerizable monomer (b) is preferably 10 to 60 mass % and morepreferably 15 to 50 mass %. By setting the content to 10 mass % orhigher, good hydrolyzability of the resin tends to be ensured, and bysetting the content to 60 mass % or lower, good flexibility of thecoating film tends to be ensured.

In addition, a ratio of content in hydrolyzable resin (ii) between thetotal content of the constitutional unit derived from silicon-containingpolymerizable monomer (a) and triorganosilyl(meth)acrylate (c) above andthe constitutional unit derived from metal-atom-containing polymerizablemonomer (b) is preferably within a range from 10/90 to 90/10 (a massratio).

Hydrolyzable resin (ii) may include a constitutional unit derived frommonomer component (d) other than silicon-containing polymerizablemonomer (a), triorganosilyl (meth)acrylate (c), andmetal-atom-containing polymerizable monomer (b) above, as inhydrolyzable resin (i). Details of other monomer components (d) are asdescribed in connection with hydrolyzable resin (i).

Hydrolyzable resin (ii) can be produced with a method similar to themethod shown in connection with hydrolyzable resin (i).

A content of the hydrolyzable resin (the total content of hydrolyzableresins (i) and (ii)) is preferably 30 to 97 mass % in a solid contentcontained in the colored antifouling paint (hereinafter referred to as apaint solid content). When the content is less than 30 mass %,adhesiveness of a coating film to an underlying substrate tends to lowerand an antifouling effect does not tend to sufficiently be exhibited.When the content exceeds 97 mass %, resistance to cracking of thecoating film tends to lower.

(B) Color Pigment

Various conventionally known color pigments can be used as a colorpigment to be contained in the colored antifouling paint, and a coloredantifouling paint with various color tones can be realized depending onselection of a color pigment (a colored antifouling paint can be variousin color). The colored antifouling paint used in the present inventioncan be free from an antifouling agent or an amount of addition thereofcan significantly be reduced. In addition, since transparency of thehydrolyzable resin is high, a sharp color tone derived from the colorpigment is provided substantially as it is. As described above, colordifference between the colored antifouling paint and a surface of anobject to be coated can thus be made great and a film thicknessdetermination function is improved.

A wider variation of colors of the colored antifouling paint increases adegree of freedom in color of the surface of the object to be coated towhich the method according to the present invention is applicable.Depending on a color tone of the colored antifouling paint, a colordifference ΔE3 between the colored antifouling paint and the surface ofthe object to be coated does not become so great for a certainparticular object to be coated, and the colored antifouling paint maynot be suitable for the method according to the present invention. Evenin such a case, this colored antifouling paint is applicable to otherobjects to be coated having a surface color sufficiently great in colordifference ΔE3 between the colored antifouling paint and the surface ofthe object to be coated. In other words, a type of the color pigment tobe added to the colored antifouling paint (a color tone of the coloredantifouling paint) can be selected in accordance with a surface color ofthe object to be coated. As described above, since a color of thecolored antifouling paint used in the present invention can be various,a colored antifouling paint sufficiently great in color difference ΔE3from the surface of the object to be coated can be prepared, whichevercolor the surface of the object to be coated may substantially have.

Specific examples of the color pigments include titanium oxide,zirconium oxide, basic lead sulfate, tin oxide, carbon black, whitelead, graphite, zinc sulfide, zinc oxide, chromium oxide, nickeltitanium yellow, chromium titanium yellow, yellow iron oxide, red ironoxide, black iron oxide, azo-based red and yellow pigments, chromeyellow, phthalocyanine green, phthalocyanine blue, ultramarine blue,quinacridone, and the like. These color pigments may be used alone or incombination of two or more types.

A content of the color pigment can be, for example, not less than 0.3mass % in the paint solid content. Though an upper limit of the contentof the color pigment is not particularly limited, it is set, forexample, to 30 mass % or lower.

(C) Antifouling Agent

The antifouling coating film obtained with the colored antifouling paintabove exhibits good antifouling performance owing to an antifoulingeffect based on hydrolyzable resin (i) and/or hydrolyzable resin (ii)above. In order to further enhance antifouling performance or furtherenhance long-term sustainment of an antifouling property, an antifoulingagent may be optionally blended in the colored antifouling paint. Anantifouling agent is not particularly limited, and a known antifoulingagent can be used. Examples thereof include an inorganic compound, anorganic compound containing a metal, an organic compound not containinga metal, and the like.

Specific examples of the antifouling agents above include: zinc oxide;cuprous oxide; manganese ethylene bisdithiocarbamate; zincdimethyldithiocarbamate;2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine;2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyldichlorophenyl urea;zinc ethylene bisdithiocarbamate; copper rhodanide (cuprousthiocyanate);4,5-dichloro-2-n-octyl-4-isothiazoline-3-one(4,5-dichloro-2-n-octyl-3(2H)isothiazolone);N-(fluorodichloromethylthio)phthalimide;N,N′-dimethyl-N′-phenyl-(N-fluorodichloromethylthio)sulfamide; such ametallic salt as 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione) andcopper salt (copper pyrithione); tetramethylthiuram disulfide;2,4,6-trichlorophenyl maleimide;2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; 3-iodo-2-propylbutylcarbamate; diiodo methyl-p-trisulfone; phenyl(bispyridyl)bismuthdichloride; 2-(4-thiazolyl)-benzimidazole; triphenylboron pyridine salt;stearylamine-triphenylboron; laurylamine-triphenylboron;bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate;1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfenamide;1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methyphenyl)methanesulfenamide;N′-(3,4-dichlorophenyl)-N,N-dimethylurea;N′-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine;and4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,and the like. These antifouling agents may be used alone or incombination of two or more types.

A content of the antifouling agent is preferably not more than 10 mass %and more preferably not more than 8 mass % in the paint solid content.When the content of the antifouling agent exceeds 10 mass %, suchdefects as cracks or peel-off may occur in the antifouling coating film.As described above, in the colored antifouling paint used in the presentinvention, hydrolyzable resins (i) and (ii) themselves have goodantifouling performance based on their own hydrolyzability and thesilicon-containing group, and an amount of blending a separateantifouling agent can be reduced or the colored antifouling paint can befree from a separate antifouling agent. Thus, a colored antifoulingpaint having further improved color sharpness, color variation, and filmthickness determination function can be realized.

(D) Thermoplastic Resin and/or Plasticizer

The colored antifouling paint above may contain a thermoplastic resinand/or a plasticizer. By containing a thermoplastic resin and/or aplasticizer, resistance to cracking of a coating film can be improved.In addition, since a polishing rate (a polishing speed) of the coatingfilm can be controlled to a moderate speed, the coating film isadvantageous also in terms of a long-term antifouling property. Inparticular, in a case where hydrolyzable resin (i) is employed as a maincomponent of the hydrolyzable resin, a thermoplastic resin and/or aplasticizer are (is) preferably used together. For example, in a casewhere an object to be coated is a marine vessel or the like, theantifouling coating film is repeatedly exposed to a cycle of immersionin water (such as seawater) for a long period and landing afterimmersion in water for a certain period, and therefore the antifoulingcoating film is required to have flexibility with which it can withstandsuch a condition. Thus, resistance to cracking is an importantcharacteristic required of the coating film.

Examples of the thermoplastic resins above include: chlorinatedparaffin; chlorinated polyolefin such as chlorinated rubber, chlorinatedpolyethylene, and chlorinated polypropylene; polyvinyl ether;polypropylene sebacate; partially hydrogenated terphenyl; polyvinylacetate; poly(meth)acrylic alkyl esters such as amethyl-(meth)acrylate-based copolymer, an ethyl-(meth)acrylate-basedcopolymer, a propyl-(meth)acrylate-based copolymer, abutyl-(meth)acrylate-based copolymer, and acyclohexyl-(meth)acrylate-based copolymer; polyether polyol; an alkydresin; a polyester resin; vinyl-chloride-based resins such as a vinylchloride-vinyl acetate copolymer, a vinyl chloride-vinyl propionatecopolymer, a vinyl chloride-isobutyl vinyl ether copolymer, a vinylchloride-isopropyl vinyl ether copolymer, and a vinyl chloride-ethylvinyl ether copolymer; a silicone oil; a wax; Vaseline; liquid paraffin;rosin, hydrogenated rosin, naphthenic acid, an aliphatic acid, and adivalent metal salt thereof; and the like. These thermoplastic resinsmay be used alone or in combination of two or more types.

Among the above, chlorinated paraffin, polyvinyl ether, polyetherpolyol, rosin, and a vinyl chloride-isobutyl vinyl ether copolymer arepreferred, and in particular, chlorinated paraffin, polyvinyl ether,rosin, and a vinyl chloride-isobutyl vinyl ether copolymer are morepreferably employed because they are suitable for adjustment ofplasticity of a coating film and an amount of consumption of the coatingfilm.

Examples of the plasticizers include: phthalate-ester-based plasticizerssuch as dioctyl phthalate (DOP), dimethyl phthalate, dicyclohexylphthalate, and di-isodecyl phthalate (DIDP); analiphatic-dibasic-acid-ester-based plasticizer such as isobutyl adipateand dibutyl sebacate; glycol-ester-based plasticizers such as diethyleneglycol dibenzoate and pentaerythritol alkyl ester;phosphoric-ester-based plasticizers such as tricresyl phosphate, triarylphosphate, and trichloroethyl phosphate; epoxy-based plasticizers suchas epoxy soybean oil and octyl epoxy stearate; organic-tin-basedplasticizers such as dioctyltin laurate and dibutyltin laurate; trioctyltrimellitate, triacethylene, and the like. These plasticizers may beused alone or in combination of two or more types.

Among the above, phthalate-ester-based plasticizers such as dioctylphthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate, anddi-isodecyl phthalate (DIDP), and phosphoric-ester-based plasticizerssuch as tricresyl phosphate, triaryl phosphate, and trichloroethylphosphate are preferably employed because they are particularlyexcellent in compatibility with the hydrolyzable resin above and thethermoplastic resin above and are able to homogenously improveresistance to cracking over the entire coating film.

The colored antifouling paint above may contain only a thermoplasticresin, may contain only a plasticizer, or may contain both of athermoplastic resin and a plasticizer. Use of a thermoplastic resin anda plasticizer together is preferred because a coating film furtherexcellent in strength and plasticity can be obtained.

Though a content of the thermoplastic resin and the plasticizer is notparticularly restricted, the content can be set, for example, to 0 to100 parts by mass with respect to 100 parts by mass of the hydrolyzableresin above, respectively, and the content is preferably set to 5 to 50parts by mass, respectively.

In addition, the total content of the thermoplastic resin and theplasticizer is preferably within a range from 3 to 100 parts by mass andmore preferably from 5 to 50 parts by mass with respect to 100 parts bymass of the hydrolyzable resin above. When the total content of thethermoplastic resin and the plasticizer is less than 3 parts by masswith respect to 100 parts by mass of the hydrolyzable resin, an effectof improvement in resistance to cracking resulting from addition of thethermoplastic resin and/or the plasticizer does not tend to be seen.When the total content of the thermoplastic resin and the plasticizer isextremely small or they are not contained, a moderate polishing rate(polishing speed) may not be obtained and a long-term antifoulingproperty may not be provided. When the total content of thethermoplastic resin and the plasticizer exceeds 100 parts by mass withrespect to 100 parts by mass of the hydrolyzable resin, adhesiveness ofa coating film to an underlying substrate tends to lower and anantifouling property tends to lower.

(E) Other Additives

The colored antifouling paint may contain other additives such as anextender pigment, a solvent, a water binder, an anti-sagging agent, ananti-floating agent, an anti-settling agent, a defoaming agent, acoating film consumption control agent, a UV absorber, a surface controlagent, a viscosity control agent, a leveling agent, a pigmentdispersant, and an antifouling agent elution control agent. A content ofthese other additives is preferably set to such an extent that a sharpcolor tone of the color pigment or the color pigment's performance ofhiding an underlying substrate is not interfered and a film thicknessdetermination function of the colored antifouling paint is not lowered.

Examples of the extender pigments above include barium sulfate, talc,clay, chalk, silica white, alumina white, bentonite, calcium carbonate,magnesium carbonate, silica, silicate, aluminum oxide hydrate, calciumsulfate, and the like. These extender pigments may be used alone or incombination of two or more types.

Examples of the solvents include: hydrocarbons such as toluene, xylene,ethylbenzene, cyclopentane, octane, heptane, cyclohexane, and whitespirit; ethers such as dioxane, tetrahydrofuran, ethyleneglycolmonomethyl ether, ethyleneglycol monoethyl ether, ethyleneglycolmonobutyl ether, ethyleneglycol dibutyl ether, diethyleneglycolmonomethyl ether, and diethyleneglycol monoethyl ether; esters such asbutyl acetate, propyl acetate, benzyl acetate, ethyleneglycol monomethylether acetate, and ethyleneglycol monoethyl ether acetate; ketones suchas ethyl isobutyl ketone and methyl isobutyl ketone; alcohols such asn-butanol and propyl alcohol; and the like. These solvents may be usedalone or in combination of two or more types.

It is noted that the colored antifouling paint above may contain othervehicle components than hydrolyzable resin (i), (ii) above and that acontent thereof is preferably minimized.

The colored antifouling paint can be prepared, for example, by addingthe color pigment and the antifouling agent, the thermoplastic resinand/or the plasticizer, and optionally other additives to thehydrolyzable resin above or a resin composition containing the same andthen mixing the mixture by using such a mixer as a ball mill, a pebblemill, a roll mill, a sand-grinding mill, a high-speed disperser.

<Film Thickness Determination Function of Colored Antifouling Paint>

The colored antifouling paint employed in the present invention is anantifouling paint excellent in film thickness determination function,which satisfies at least conditions (a) and (b) below and preferablyfurther satisfies a condition (d) below:

(a) A coating film formed from the colored antifouling paint having atarget dry film thickness T completely hides a surface of an object tobe coated;

(b) Color difference ΔE1 between a coating film formed from the coloredantifouling paint having the target dry film thickness T and a coatingfilm formed from the colored antifouling paint having a dry filmthickness of 0.8 T is not lower than 2.0; and

(d) Color difference ΔE2 between a coating film formed from the coloredantifouling paint having the target dry film thickness T and a coatingfilm formed from the colored antifouling paint having a dry filmthickness of 1.2 T is less than 1.

Color differences ΔE1 and ΔE2 as well as ΔE3 which will be describedlater can be measured with a generally employed method, by using such acolor difference meter (a colorimeter) as a tristimulus colorimeter SMcolor meter (model number SM-T45 manufactured by Suga Test InstrumentsCo., Ltd., JIS Z8722). Color differences ΔE1, ΔE2, and ΔE3 are eachindicated by an absolute value.

The condition (a) above defines an ability for a coating film formedfrom the colored antifouling paint to hide a surface of an object to becoated (the coating film herein refers to a dry coating film, however, awet coating film and a dry coating film are substantially the same inability to hide an underlying substrate). As the surface of the objectto be coated is coated with the colored antifouling paint and as athickness of the coating film increases, a degree of “see-through” ofthe surface of the object to be coated becomes lower. It is determinedthat the coating film formed from the colored antifouling paintcompletely hides the surface of the object to be coated when a colortone of the surface of the object to be coated disappears and the colortone of a coated surface becomes the same as the color tone of thecoating film formed from the colored antifouling paint. The coloredantifouling paint employed in the present invention can achieve suchcomplete hiding of the surface of the object to be coated when a drycoating film not smaller than the target dry film thickness T is formed.

The condition (b) above defines color difference ΔE1 between the drycoating film formed from the colored antifouling paint having the targetdry film thickness T and the dry coating film having the dry filmthickness of 0.8 T. The coating film having the dry coating filmthickness of 0.8 T is a coating film immediately before painting iscompleted. Therefore, with great color difference ΔE1 being not smallerthan 2.0, dependence on a film thickness, of a color tone of a coatingfilm just before painting is completed (from immediately before thetarget dry film thickness T (0.8 T) to the target dry film thickness T)becomes great, and therefore a dry coating film having the target dryfilm thickness T can extremely accurately be formed and even smallshortage in film thickness can be avoided. Color difference ΔE1 ispreferably not smaller than 2.5. It is noted that too great colordifference ΔE1 is likely to cause mottled color due to even a smalldifference in film thickness, and hence color difference ΔE1 ispreferably not greater than 10 and more preferably not greater than 5.Color difference ΔE1 “not smaller than 2.0” and further “not smallerthan 2.5” was realized by using hydrolyzable resin(s) (i) and/or (ii) asthe hydrolyzable resin and it could not be achieved with a conventionalhydrolyzable resin.

It is noted that the target dry film thickness T can be selected asappropriate in consideration of an antifouling property or the likerequired of an object to be coated, and it is not particularly limited.For example, the target dry film thickness T can be approximately notsmaller than 30 μm and not greater than 300 μm with a dry film thicknessof one coat (one layer of an antifouling coating film formed by applyingthe method according to the present invention).

The condition (d) above defines color difference ΔE2 between the drycoating film formed from the colored antifouling paint having the targetdry film thickness T and a dry coating film having the dry filmthickness of 1.2 T. The coating film having the dry coating filmthickness of 1.2 T is a coating film immediately after painting wascompleted. When color difference ΔE2 is equal to or greater than 1,color difference between the coating film having the target dry filmthickness T and the coating film having a thickness exceeding the targetdry film thickness T is great, which is likely to cause mottled color.Color difference ΔE2 is preferably not greater than 0.5 and furtherpreferably not greater than 0.4.

Color difference ΔE3 between the colored antifouling paint itself andthe surface of an object to be coated is preferably greater than 0 andmore preferably not smaller than 5. As color difference ΔE3 is greater,how a color difference from the object to be coated changes can readilyvisually be checked as the thickness of the coating film being appliedis closer to the target film thickness. Namely, when color differenceΔE3 is too small, it becomes difficult to check whether or not thecoating film has completely hidden the surface of the object to becoated and a coating film having the target dry film thickness T is lesslikely to be obtained. According to the present invention, sincehydrolyzable resin(s) (i) and/or (ii) are (is) employed as a vehicle, acolored antifouling paint great in color difference ΔE3 can readily beobtained.

The colored antifouling paint satisfying the conditions above can beobtained by selecting a type of the color pigment (a color tone) andadjusting a content thereof, on the premise that hydrolyzable resin(s)(i) and/or (ii) are (is) employed as a vehicle. The target dry filmthickness T of the colored antifouling paint can be adjusted inaccordance with a content of the color pigment. Namely, basically, bydecreasing a content of the color pigment, the target dry film thicknessT of the colored antifouling paint can be increased. In other words,since the target dry film thickness T is determined by characteristicsof a coating film such as antifouling performance, resistance tocracking, and the like required of the coating film, a type of an objectto be coated, and the like, a content of the color pigment is adjustedin accordance with the prescribed target dry film thickness T.

Alternatively, the colored antifouling paint employed in the presentinvention may be prepared by mixing two or more types of coloredantifouling paints different in the target dry film thickness T(different in content of the color pigment) (the colored antifoulingpaints are according to the present invention and satisfy the conditions(a) to (c) above and preferably further satisfy (d)). With such apreparation method, a colored antifouling paint having a target dry filmthickness different from a target dry film thickness of a mixed coloredantifouling paints can readily be obtained. With this method, the targetdry film thickness T of an obtained colored antifouling paint can beadjusted based on a mixing ratio of the colored antifouling paints to bemixed.

<Method of Forming Antifouling Coating Film>

According to the method of the present invention, the surface of theobject to be coated is coated with the colored antifouling paint abovewhile change in color difference between the coating film being appliedand the surface of the object to be coated is observed. “Observingchange in color difference between the coating film being applied andthe surface of the object to be coated” typically refers to observationof whether “see-through” of the surface of the object to be coated takesplace in the coated surface, that is, to which degree the coating filmbeing applied (wet coating film) hides the surface of the object to becoated, and in the present invention, coating is carried out until thecolor tone of the coated surface becomes the same as the color tone ofthe coating film formed from the colored antifouling paint, that is,until the coating film formed from the colored antifouling paintcompletely hides the surface of the object to be coated. Since anability for the wet coating film to hide an underlying substrate issubstantially the same as that for the dry coating film, a thickness ofthe wet coating film at the time of complete hiding is comparable to afilm thickness corresponding to the target dry film thickness. Here,since the colored antifouling paint employed in the present inventionsatisfies the condition (b) above, the color difference between thecoating film immediately before painting is completed and the filmthickness of the wet coating film corresponding to the target drycoating film is great and hence the dry coating film having the targetdry film thickness can extremely accurately be formed. Whether thecoating film formed from the colored antifouling paint completely hidesthe surface of the object to be coated or not can readily visually bechecked.

According to the method of forming the antifouling coating film of thepresent invention as shown above, a uniform antifouling coating filmhaving a prescribed dry film thickness can be formed more accuratelythan in the conventional method.

The antifouling coating film can be formed by coating the surface of theobject to be coated with the colored antifouling paint above with anordinary method and thereafter volatilizing and removing a solvent atroom temperature or under heating as necessary. A coating method is notparticularly limited, and conventionally known methods such asimmersion, spraying, brush painting, roller painting, electrostaticpainting, electropainting, and the like are exemplified.

The object to be coated is not particularly limited, and examplesthereof include various structures, in particular underwater structures,made, for example, of steel materials such as a non-treated steelmaterial, a blasted steel material, an acid-treated steel material, azinc-plated steel material, and a stainless steel material, nonferrousmetal materials such as an aluminum (alloy) material and a copper(alloy) material, concrete, plastic, and the like. These steel materialsand nonferrous metal materials may include a weld line. Specificexamples of the object to be coated include an underwater structure suchas marine vessels, harbor facilities, an intake structure such as apower plant, a pipe such as an aqueduct for cooling, a bridge, abuoyage, industrial water facilities, and a sea bottom base.

A surface of an object to be coated, which is to be coated with thecolored antifouling paint, may be pre-treated as necessary or may havean undercoat coating film formed from an anti-corrosive paint, otherantifouling paints, a binder paint for improving adhesiveness of acoating film formed from the colored antifouling paint, or the like. Apaint forming the undercoat coating film may be an old coating film thathas been used. In this case, the method according to the presentinvention may be applied for repair of the old coating film. Otherantifouling paints above may be a colored antifouling paint according tothe present invention different in color from the colored antifoulingpaint for coating, in addition to the conventionally known antifoulingpaints. In addition, the antifouling paint forming the undercoat coatingfilm may have a color tone the same as that of the colored antifoulingpaint so long as the color tone of the undercoat coating film creates asufficiently great color difference (a color difference corresponding toΔE3 above) from the colored antifouling paint formed thereon. In a casewhere an undercoat coating film is formed on the surface of the objectto be coated, the “surface of the object to be coated” in the condition(a) above means the surface of the undercoat coating film.

EXAMPLES

Though the present invention will be described hereinafter in furtherdetail with reference to Examples and Comparative Examples, the presentinvention is not limited thereto.

[1] Preparation of Metal-Atom-Containing Polymerizable Monomer (b)

Producing Example M1 Preparation of Metal-Atom-Containing PolymerizableMonomer Mixture M1

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 85.4 parts by mass of PGM (propyleneglycol methylether) and 40.7 parts by mass of zinc oxide were loaded, and atemperature thereof was raised to 75° C. while they were stirred. Then,a mixture composed of 43.1 parts by mass of methacrylic acid, 36.1 partsby mass of acrylic acid, and 5 parts by mass of water was dropped at aconstant velocity in 3 hours from the dropping funnel. After furtherstirring for 2 hours, 36 parts by mass of PGM were added to therebyobtain a transparent metal-atom-containing polymerizable monomer mixtureM1. A solid content was 44.8 mass %. This metal-atom-containingpolymerizable monomer mixture M1 contains as metal-atom-containingpolymerizable monomer (b), zinc di(meth)acrylate which is monomer (b2).

Producing Example M2 Preparation of Metal-Atom-Containing PolymerizableMonomer Mixture M2

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 72.4 parts by mass of PGM and 40.7 parts by massof zinc oxide were loaded, and a temperature thereof was raised to 75°C. while they were stirred. Then, a mixture composed of 30.1 parts bymass of methacrylic acid, 25.2 parts by mass of acrylic acid, and 51.6parts by mass of versatic acid was dropped at a constant velocity in 3hours from the dropping funnel. After further stirring for 2 hours, 11parts by mass of PGM were added to thereby obtain a transparentmetal-atom-containing polymerizable monomer mixture M2. A solid contentwas 59.6 mass %. This metal-atom-containing polymerizable monomermixture M2 contains as metal-atom-containing polymerizable monomer (b),zinc (meth)acrylate which is monomer (b1) expressed in the generalformula (VP) above (R³⁰ being a versatic acid residue) and zincdi(meth)acrylate which is monomer (b2).

(Producing Example M3: Preparation of Metal-Atom-ContainingPolymerizable Monomer Mixture M3)

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 60 parts by mass of xylene, 13 parts by mass ofPGM, and 40.7 parts by mass of zinc oxide were loaded, and a temperaturethereof was raised to 75° C. while they were stirred. Then, a mixturecomposed of 32.3 parts by mass of methacrylic acid, 27 parts by mass ofacrylic acid, 37.7 parts by mass of oleic acid, 2.3 parts by mass ofacetic acid, and 5.8 parts by mass of propionic acid was dropped at aconstant velocity in 3 hours from the dropping funnel. After furtherstirring for 2 hours, 77 parts by mass of xylene and 46 parts by mass ofPGM were added to thereby obtain a transparent metal-atom-containingpolymerizable monomer mixture M3. A solid content was 39.6 mass %. Thismetal-atom-containing polymerizable monomer mixture M3 contains asmetal-atom-containing polymerizable monomer (b), zinc (meth)acrylatewhich is monomer (b1) expressed in the general formula (VI′) above (R³⁰being one or more types of an oleic acid residue, an acetic acidresidue, and a propionic acid residue) and zinc di(meth)acrylate whichis monomer (b2).

[2] Preparation of Hydrolyzable Resin (i)

(Producing Example S1: Preparation of Hydrolyzable Resin Composition S1)

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 65 parts by mass ofxylene and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 32.3 parts by mass of methyl methacrylate, 43.9parts by mass of ethyl acrylate, 10 parts by mass of “FM-0721”(manufactured by Chisso Corporation), 21.7 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.2 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass ofazobisisobutyronitrile (AIBN), and 3 parts by mass ofazobismethylbutyronitrile (AMBN) was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.1 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S1.

Obtained hydrolyzable resin composition S1 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S1was 6800 in terms of polystyrene. In addition, the hydrolyzable resinisolated by reprecipitation using methanol from obtained hydrolyzableresin composition S1 was taken into a platinum crucible, to whichsulfuric acid was added, and the mixture was placed in a pressuredecomposition container for heating. After sulfuric acid wasvolatilized, the hydrolyzable resin was completely incinerated. Thisincinerated substance was let stand to cool and then fused with alkali.The resulting product was analyzed with an ICP emission spectroscopicapparatus (“SPS5100” manufactured by Seiko Instruments Inc.), and thenSi atoms were detected. In addition, the hydrolyzable resin was analyzedwith an atomic absorption spectrophotometer (“AA6300” manufactured byShimadzu Corporation) and a signal derived from Zn atoms was detected.

Producing Example S2 Preparation of Hydrolyzable Resin Composition S2

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 65 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 32.3 parts by mass of methyl methacrylate, 13.9parts by mass of ethyl acrylate, 40 parts by mass of “FM-0711”(manufactured by Chisso Corporation), 21.7 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.2 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 0.8 part by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.1 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S2.

Obtained hydrolyzable resin composition S2 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S2was 8800 in terms of polystyrene.

Producing Example S3 Preparation of Hydrolyzable Resin Composition S3

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM and 61 parts by mass ofxylene were loaded, and a temperature thereof was raised to 100° C.while they were stirred. Then, a mixture composed of 18 parts by mass ofmethyl methacrylate, 25 parts by mass of ethyl acrylate, 40 parts bymass of “X-24-8201” (manufactured by Shin-Etsu Chemical Co., Ltd.), 28.4parts by mass of metal-atom-containing polymerizable monomer mixture M2in Producing Example M2 above, 20 parts by mass of PGM, 2.5 parts bymass of AIBN, and 1 part by mass of AMBN was dropped at a constantvelocity in 4 hours from the dropping funnel. After dropping ended, 0.5part by mass of t-butyl peroctoate and 10 parts by mass of xylene weredropped in 30 minutes followed by further stirring for 1 hour and 30minutes. Thereafter, 4.6 parts by mass of xylene were added to therebyobtain hydrolyzable resin composition S3.

Obtained hydrolyzable resin composition S3 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S3was 8200 in terms of polystyrene.

Producing Example 54 Preparation of Hydrolyzable Resin Composition S4

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 35 parts by mass of PGM and 41 parts by mass ofxylene were loaded, and a temperature thereof was raised to 100° C.while they were stirred. Then, a mixture composed of 18 parts by mass ofmethyl methacrylate, 15 parts by mass of ethyl acrylate, 50 parts bymass of “X-24-8201” (manufactured by Shin-Etsu Chemical Co., Ltd.), 42.5parts by mass of metal-atom-containing polymerizable monomer mixture M3in Producing Example M3 above, 5 parts by mass of PGM, 2.5 parts by massof AIBN, and 1 part by mass of AMBN was dropped at a constant velocityin 6 hours from the dropping funnel. After dropping ended, 0.5 part bymass of t-butyl peroctoate and 10 parts by mass of xylene were droppedin 30 minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 5.5 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S4.

Obtained hydrolyzable resin composition S4 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S4was 7200 in terms of polystyrene.

Producing Example S5 Preparation of Hydrolyzable Resin Composition S5

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 59 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 26.4 parts by mass of methyl methacrylate, 25.5parts by mass of ethyl acrylate, 30 parts by mass of asilicon-containing monomer A, 31.3 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.5 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 4 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.8 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S5.

Obtained hydrolyzable resin composition S5 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S5was 6400 in terms of polystyrene.

Producing Example S6 Preparation of Hydrolyzable Resin Composition S6

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 59 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 21.4 parts by mass of methyl methacrylate, 25.5parts by mass of ethyl acrylate, 5 parts by mass of styrene, 30 parts bymass of a silicon-containing monomer B, 31.3 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.5 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 2.5 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.8 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S6.

Obtained hydrolyzable resin composition S6 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S6was 6900 in terms of polystyrene.

Producing Example S7 Preparation of Hydrolyzable Resin Composition S7

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 59 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 26.4 parts by mass of methyl methacrylate, 14.5parts by mass of ethyl acrylate, 5 parts by mass of 2-methoxyethylacrylate, 20 parts by mass of “FM-0711” (manufactured by ChissoCorporation), 20 parts by mass of “TM-0701” (manufactured by ChissoCorporation), 31.3 parts by mass of metal-atom-containing polymerizablemonomer mixture M1 in Producing Example M1 above, 10 parts by mass ofxylene, 1.5 parts by mass of the chain transfer agent α-methylstyrenedimer), 2.5 parts by mass of AIBN, and 2.5 parts by mass of AMBN wasdropped at a constant velocity in 6 hours from the dropping funnel.After dropping ended, 0.5 part by mass of t-butyl peroctoate and 10parts by mass of xylene were dropped in 30 minutes followed by furtherstirring for 1 hour and 30 minutes. Thereafter, 10.8 parts by mass ofxylene were added to thereby obtain a hydrolyzable resin composition S7.

Obtained hydrolyzable resin composition S7 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S7was 7000 in terms of polystyrene.

Producing Example S8 Preparation of Hydrolyzable Resin Composition S8

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM and 61 parts by mass ofxylene were loaded, and a temperature thereof was raised to 100° C.while they were stirred. Then, a mixture composed of 18 parts by mass ofmethyl methacrylate, 35 parts by mass of ethyl acrylate, 30 parts bymass of a silicon-containing monomer C, 28.4 parts by mass ofmetal-atom-containing polymerizable monomer mixture M2 in ProducingExample M2 above, 20 parts by mass of PGM, 2.5 parts by mass of AIBN,and 2 parts by mass of AMBN was dropped at a constant velocity in 4hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 4.6 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S8.

Obtained hydrolyzable resin composition S8 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S8was 7700 in terms of polystyrene.

Producing Example S9 Preparation of Hydrolyzable Resin Composition S9

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 59 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 26.4 parts by mass of methyl methacrylate, 35.5parts by mass of ethyl acrylate, 20 parts by mass of asilicon-containing monomer D, 31.3 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.5 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 5.5 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.8 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S9.

Obtained hydrolyzable resin composition S9 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin composition S9was 6000 in terms of polystyrene.

Producing Example S10 Preparation of Hydrolyzable Resin Composition S10

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 65 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 32.3 parts by mass of methyl methacrylate, 43.9parts by mass of ethyl acrylate, 10 parts by mass of “FM-7711”(manufactured by Chisso Corporation), 21.7 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 2 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 7.5 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.1 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S10.

Obtained hydrolyzable resin composition S10 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS10 was 5400 in terms of polystyrene. In addition, the hydrolyzableresin isolated by reprecipitation using methanol from obtainedhydrolyzable resin composition S10 was taken into a platinum crucible,to which sulfuric acid was added, and the mixture was placed in apressure decomposition container for heating. After sulfuric acid wasvolatilized, the hydrolyzable resin was completely incinerated. Thisincinerated substance was let stand to cool and then fused with alkali.The resulting product was analyzed with an ICP emission spectroscopicapparatus (“SPS5100” manufactured by Seiko Instruments Inc.), and thenSi atoms were detected. In addition, the hydrolyzable resin was analyzedwith an atomic absorption spectrophotometer (“AA6300” manufactured byShimadzu Corporation) and a signal derived from Zn atoms was detected.

Producing Example S11 Preparation of Hydrolyzable Resin Composition S11

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 65 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 32.3 parts by mass of methyl methacrylate, 33.9parts by mass of ethyl acrylate, 20 parts by mass of “FM-7721”(manufactured by Chisso Corporation), 21.7 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.5 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 5 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.1 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S11.

Obtained hydrolyzable resin composition S11 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS11 was 6200 in terms of polystyrene.

Producing Example S12 Preparation of Hydrolyzable Resin Composition S12

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 59 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 26.4 parts by mass of methyl methacrylate, 40.5parts by mass of ethyl acrylate, 15 parts by mass of asilicon-containing monomer E, 31.3 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 2 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 8 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.8 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S12.

Obtained hydrolyzable resin composition S12 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS12 was 5600 in terms of polystyrene.

Producing Example S13 Preparation of Hydrolyzable Resin Composition S13

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 59 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 26.4 parts by mass of methyl methacrylate, 35.5parts by mass of ethyl acrylate, 20 parts by mass of asilicon-containing monomer F, 31.3 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.5 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 7.5 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.8 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S13.

Obtained hydrolyzable resin composition S13 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS13 was 5500 in terms of polystyrene.

Producing Example S14 Preparation of Hydrolyzable Resin Composition S14

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 65 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 32.3 parts by mass of methyl methacrylate, 13.9parts by mass of ethyl acrylate, 5 parts by mass of “FM-7711”(manufactured by Chisso Corporation), 35 parts by mass of “FM-0711”(manufactured by Chisso Corporation), 21.7 parts by mass ofmetal-atom-containing polymerizable monomer mixture M1 in ProducingExample M1 above, 10 parts by mass of xylene, 1.2 parts by mass of thechain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN,and 4 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 10.1 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S14.

Obtained hydrolyzable resin composition S14 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS14 was 9000 in terms of polystyrene.

Producing Example S15 Preparation of Hydrolyzable Resin Composition S15

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 35 parts by mass of PGM and 31 parts by mass ofxylene were loaded, and a temperature thereof was raised to 100° C.while they were stirred. Then, a mixture composed of 18 parts by mass ofmethyl methacrylate, 25 parts by mass of ethyl acrylate, 10 parts bymass of “FM-7721” (manufactured by Chisso Corporation), 30 parts by massof “X-24-8201” (manufactured by Shin-Etsu Chemical Co., Ltd.), 28.4parts by mass of metal-atom-containing polymerizable monomer mixture M2in Producing Example M2 above, 30 parts by mass of xylene, 2.5 parts bymass of AIBN, and 2.5 parts by mass of AMBN was dropped at a constantvelocity in 4 hours from the dropping funnel. After dropping ended, 0.5part by mass of t-butyl peroctoate and 10 parts by mass of xylene weredropped in 30 minutes followed by further stirring for 1 hour and 30minutes. Thereafter, 4.6 parts by mass of xylene were added to therebyobtain a hydrolyzable resin composition S15.

Obtained hydrolyzable resin composition S15 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS15 was 7200 in terms of polystyrene.

Producing Example S16 Preparation of Hydrolyzable Resin Composition S16

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 40 parts by mass of PGM and 31 parts by mass ofxylene were loaded, and a temperature thereof was raised to 100° C.while they were stirred. Then, a mixture composed of 18 parts by mass ofmethyl methacrylate, 15 parts by mass of ethyl acrylate, 10 parts bymass of “FM-7711” (manufactured by Chisso Corporation), 10 parts by massof “FM-7721” (manufactured by Chisso Corporation), 30 parts by mass of“FM-0711” (manufactured by Chisso Corporation), 42.5 parts by mass ofmetal-atom-containing polymerizable monomer mixture M3 in ProducingExample M3 above, 10 parts by mass of xylene, 2.5 parts by mass of AIBN,and 4.5 parts by mass of AMBN was dropped at a constant velocity in 6hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 5.5 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S16.

Obtained hydrolyzable resin composition S16 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS16 was 6400 in terms of polystyrene.

Producing Example S17 Preparation of Hydrolyzable Resin Composition S17

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM, 59 parts by mass ofxylene, and 4 parts by mass of ethyl acrylate were loaded, and atemperature thereof was raised to 100° C. while they were stirred. Then,a mixture composed of 26.4 parts by mass of methyl methacrylate, 15.5parts by mass of ethyl acrylate, 2 parts by mass of a silicon-containingmonomer G, 38 parts by mass of silicon-containing monomer D, 31.3 partsby mass of metal-atom-containing polymerizable monomer mixture M1 inProducing Example M1 above, 10 parts by mass of xylene, 1.2 parts bymass of the chain transfer agent (α-methylstyrene dimer), 2.5 parts bymass of AIBN, and 5.5 parts by mass of AMBN was dropped at a constantvelocity in 6 hours from the dropping funnel. After dropping ended, 0.5part by mass of t-butyl peroctoate and 10 parts by mass of xylene weredropped in 30 minutes followed by further stirring for 1 hour and 30minutes. Thereafter, 10.8 parts by mass of xylene were added to therebyobtain a hydrolyzable resin composition S17.

Obtained hydrolyzable resin composition S17 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS17 was 5600 in terms of polystyrene.

Producing Example S18 Preparation of Hydrolyzable Resin Composition S18

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 35 parts by mass of PGM and 31 parts by mass ofxylene were loaded, and a temperature thereof was raised to 100° C.while they were stirred. Then, a mixture composed of 18 parts by mass ofmethyl methacrylate, 45 parts by mass of ethyl acrylate, 10 parts bymass of silicon-containing monomer G, 10 parts by mass of “TM-0701”(manufactured by Chisso Corporation), 28.4 parts by mass ofmetal-atom-containing polymerizable monomer mixture M2 in ProducingExample M2 above, 30 parts by mass of xylene, 2.5 parts by mass of AIBN,and 5 parts by mass of AMBN was dropped at a constant velocity in 4hours from the dropping funnel. After dropping ended, 0.5 part by massof t-butyl peroctoate and 10 parts by mass of xylene were dropped in 30minutes followed by further stirring for 1 hour and 30 minutes.Thereafter, 4.6 parts by mass of xylene were added to thereby obtain ahydrolyzable resin composition S18.

Obtained hydrolyzable resin composition S18 was analyzed with GPC(“HLC-8220GPC” manufactured by Tosoh Corporation, eluant:dimethylformamide). Then, a value for a weight-average molecular weightof the hydrolyzable resin contained in hydrolyzable resin compositionS18 was 6000 in terms of polystyrene.

Tables 1 and 2 summarize a charging amount of each raw material used forpreparation of hydrolyzable resin compositions S1 to S18 above (parts bymass), Gardner viscosity (measured at 25° C. with the use of a Gardnerbubble viscometer) and a solid content (mass %) of hydrolyzable resincompositions S1 to S18, as well as a weight-average molecular weight ofthe hydrolyzable resins contained in the compositions.

TABLE 1 Producing Example S1 S2 S3 S4 S5 S6 S7 S8 S9 Charging (a) (a1)FM-0711 40 20 Amount FM-0721 10 (Parts by X-24-8201 40 50 Mass) Silicon-30 Containing Monomer A Silicon- 30 Containing Monomer B (a2) TM-0701 20Silicon- 30 Containing Monomer C Silicon- 20 Containing Monomer D (b)Metal-Atom- M1 21.7 21.7 31.3 31.3 31.3 31.3 Containing M2 28.4 28.4Monomer Mixture M3 42.5 (d) MMA 32.3 32.3 18 18 26.4 21.4 26.4 18 26.4EA 43.9 17.9 25 15 29.5 29.5 18.5 35 39.5 2-MTA 5 ST 5 Initiator AIBN2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 AMBN 3 0.8 1 1 4 2.5 2.5 2 5.5 ChainTransfer Nofmer 1.2 1.2 1.5 1.5 1.5 1.5 Agent MSD Gardner Viscosity −U+U +U +R −W −T −V +T +W Solid Content (Mass %) 45.7 45.1 45.2 45.0 45.845.3 45.6 45.3 45.6 Weight-Average Molecular Weight 6800 8800 8200 72006400 6900 7000 7700 6000

TABLE 2 Producing Example S10 S11 S12 S13 S14 S15 S16 S17 S18 Charging(a) (a1) FM-0711 35 30 Amount X-24-8201 30 (Parts by (a2) TM-0701 10Mass) Silicon- 38 Containing Monomer D (a3) FM-7711 10 5 10 FM-7721 2010 10 Silicon- 15 Containing Monomer E (a4) Silicon- 20 ContainingMonomer F Silicon- 2 10 Containing Monomer G (b) Metal-Atom- M1 21.721.7 31.3 31.3 21.7 31.3 Containing M2 28.4 28.4 Monomer Mixture M3 42.5(d) MMA 32.3 32.3 26.4 26.4 32.3 18 18 26.4 18 EA 47.9 37.9 44.5 39.517.9 25 15 19.5 45 Initiator AIBN 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5AMBN 7.5 5 8 7.5 4 2.5 4.5 5.5 5 Chain Transfer Nofmer 2 1.5 2 1.5 1.21.2 Agent MSD Gardner Viscosity +W +U +R −W +V −V −T −T +W Solid Content(Mass %) 46.2 46.1 46.4 45.8 45.6 45.4 45.6 45.6 45.6 Weight-AverageMolecular Weight 5400 6200 5600 5500 9000 7200 6400 5600 6000

A trade name and abbreviation shown in Tables 1 and 2 are as follows.

(1) FM-0711 (a trade name, a product of Chisso Corporation): asilicon-containing polymerizable monomer having m=0, b=3, n=10, and R¹to R⁵ and R³¹ each being a methyl group in the general formula (I′)above

(2) FM-0721 (a trade name, a product of Chisso Corporation): asilicon-containing polymerizable monomer having m=0, b=3, n=65, and R¹to R⁵ and R³¹ each being a methyl group in the general formula (I′)above

(3) X-24-8201 (a trade name, a product of Shin-Etsu Chemical Co., Ltd.):a silicon-containing polymerizable monomer having m=0, b=3, n=25, and R¹to R⁵ and R³¹ each being a methyl group in the general formula (I′)above

(4) Silicon-containing monomer A: a silicon-containing polymerizablemonomer having m=10, b=3, n=10, and R¹ to R⁵ and R³¹ each being a methylgroup in the general formula (I′) above, which is a 1:1 (molar ratio)mixture of a monomer with a being set to 2 and a monomer with a beingset to 3 (this monomer was commercially available from Nippon UnicarCo., Ltd. under a trade name “F2-254-04”)

(5) Silicon-containing monomer B: a silicon-containing polymerizablemonomer having m=4, b=3, n=10, and R¹ to R⁵ and R³¹ each being a methylgroup in the general formula (I′) above, which is a 1:1 (molar ratio)mixture of a monomer with a being set to 2 and a monomer with a beingset to 3 (this monomer was commercially available from Nippon UnicarCo., Ltd. under a trade name “F2-254-14”)

(6) TM-0701 (a trade name, a product of Chisso Corporation): asilicon-containing polymerizable monomer having p=0, d=3, and R⁶ to R⁸and R³² each being a methyl group in the general formula (II′) above

(7) Silicon-containing monomer C: a silicon-containing polymerizablemonomer having p=0, d=3, R⁶ to R⁷ and R³² each being a methyl group, andR⁸ being R^(a) (x=3, R²³ to R²⁷ each being a methyl group) in thegeneral formula (II′) above (this monomer was commercially availablefrom Nippon Unicar Co., Ltd. under a trade name “F2-302-01”)

(8) Silicon-containing monomer D: a silicon-containing polymerizablemonomer having p=10, d=3, R⁶ to R⁷ and R³² each being a methyl group,and R⁸ being R^(a) (x=3, R²³ to R²⁷ each being a methyl group) in thegeneral formula (II′) above, which is a 1:1 (molar ratio) mixture of amonomer with c being set to 2 and a monomer with c being set to 3 (thismonomer was commercially available from Nippon Unicar Co., Ltd. under atrade name “F2-302-04”)

(9) FM-7711 (a trade name, a product of Chisso Corporation): asilicon-containing polymerizable monomer having q and s=0, f and g=3,r=10, and R⁹ to R¹², R³³, and R³⁴ each being a methyl group in thegeneral formula (III′) above

(10) FM-7721 (a trade name, a product of Chisso Corporation): asilicon-containing polymerizable monomer having q and s=0, f and g=3,r=65, and R⁹ to R¹², R³³, and R³⁴ each being a methyl group in thegeneral formula (III′) above

(11) Silicon-containing monomer E: a silicon-containing polymerizablemonomer having q and s=10, f and g=3, r=10, and R⁹ to R¹², R³³, and R³⁴each being a methyl group in the general formula (III′) above, which isa 1:1 (molar ratio) mixture of a monomer with e and h being set to 2 anda monomer with e and h being set to 3 (this monomer was commerciallyavailable from Nippon Unicar Co., Ltd. under a trade name “F2-354-04”)

(12) Silicon-containing monomer F: a silicon-containing polymerizablemonomer having t and u=0, j and k=3, v and w=3, and R¹³ to R²², R³⁵, andR³⁶ each being a methyl group in the general formula (IV′) above (thismonomer was commercially available from Nippon Unicar Co., Ltd. under atrade name “F2-312-01”)

(13) Silicon-containing monomer G: a silicon-containing polymerizablemonomer having t and u=10, j and k=3, v and w=3, and R¹³ to R²², R³⁵,and R³⁶ each being a methyl group in the general formula (IV′) above,which is a 1:1 (molar ratio) mixture of a monomer with i and l being setto 2 and a monomer with i and l being set to 3 (this monomer wascommercially available from Nippon Unicar Co., Ltd. under a trade name“F2-312-04”)

(14) MMA: methyl methacrylate

(15) EA: ethyl acrylate

(16) 2-MTA: 2-methoxyethyl acrylate

(17) ST: styrene

(18) AIBN: azobisisobutyronitrile

(19) AMBN: azobismethylbutyronitrile

[3] Preparation of Hydrolyzable Resin (ii)

Producing Example S19 Preparation of Hydrolyzable Resin Composition S19

In a four-neck flask including a stirrer, a cooler, a temperaturecontrol device, a nitrogen introduction pipe, and a dropping funnel, 70parts by mass of xylene were added and kept at 100° C. In this solution,a mixture solution composed of a monomer in accordance with aformulation (parts by mass) in Table 3 and 2 parts by mass oft-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 3hours. After dropping ended, the temperature of the mixture solution waskept for 30 minutes. Thereafter, a mixture solution composed of 30 partsby mass of xylene and 0.2 part by mass of t-butylperoxy-2-ethylhexanoatewas dropped at a constant velocity for 30 minutes. After dropping ended,the temperature of the mixture solution was kept for 1.5 hours. Avarnish A was thus obtained. A solid content in obtained varnish A was50.1 mass % and viscosity was 27 poises. In addition, a number averagemolecular weight (GPC, in terms of polystyrene, to be understoodsimilarly hereafter) of the hydrolyzable resin contained in varnish Awas 15000. In Examples below, this varnish A was employed as it is as ahydrolyzable resin composition S19.

Producing Example S20 Preparation of Hydrolyzable Resin Composition S20

In a reaction vessel as in Producing Example S19 above, 80 parts by massof xylol were added and kept at 100° C. In this solution, a mixturesolution composed of a monomer in accordance with a formulation (partsby mass) in Table 3 and 1 part by mass of t-butylperoxy-2-ethylhexanoatewas dropped at a constant velocity for 3 hours. After dropping ended,the temperature of the mixture solution was kept for 30 minutes.Thereafter, a mixture solution composed of 20 parts by mass of xyleneand 0.2 part by mass of t-butylperoxy-2-ethylhexanoate was dropped at aconstant velocity for 30 minutes. After dropping ended, the temperatureof the mixture solution was kept for 1.5 hours. A varnish B was thusobtained. A solid content in obtained varnish B was 49.7 mass % andviscosity was 15 poises. In addition, a number average molecular weightof the hydrolyzable resin contained in varnish B was 10000. In Examplesbelow, this varnish B was employed as it is as a hydrolyzable resincomposition S20.

Producing Example S21 Preparation of Hydrolyzable Resin Composition S21

In a reaction vessel as in Producing Example S19 above, 64 parts by massof xylol and 16 parts by mass of n-butanol were added and kept at 100°C. In this solution, a mixture solution composed of a monomer inaccordance with a formulation (parts by mass) in Table 3 and 2 parts bymass of t-butylperoxy-2-ethylhexanoate was dropped at a constantvelocity for 3 hours. After dropping ended, the temperature of themixture solution was kept for 30 minutes. Thereafter, a mixture solutioncomposed of 16 parts by mass of xylene, 4 parts by mass of n-butanol,and 0.2 part by mass of t-butylperoxy-2-ethylhexanoate was dropped at aconstant velocity for 30 minutes. After dropping ended, the temperatureof the mixture solution was kept for 1.5 hours. A varnish C was thusobtained. A solid content in obtained varnish C was 51.2 mass % andviscosity was 10 poises. In addition, a number average molecular weightof the resin contained in varnish C was 10000 and an acid value was 70mgKOH/g.

Then, in a similar reaction vessel, 100 parts by mass of varnish C, 12.9parts by mass of copper acetate, 21.9 parts by mass of hydrogenatedrosin (Hypale CH, acid value of 160 mgKOH/g, manufactured by ArakawaChemical Industries, Ltd.), and 60 parts by mass of xylene were added, atemperature of the mixture was raised to a reflux temperature, andreaction was continued for 18 hours while a distilled mixture solutionof acetic acid, water, and a solvent was removed and xylol in the sameamount was replenished. An end point of reaction was determined byquantifying an amount of acetic acid in the distilled solvent. After thereaction solution was cooled, n-butanol and xylene were added to therebyobtain a hydrolyzable resin composition S21 having a solid content of50.6 mass %.

Producing Example S22 Preparation of Hydrolyzable Resin Composition S22

In a reaction vessel as in Producing Example S19 above, 40 parts by massof xylol and 20 parts by mass of n-butanol were added and kept at 105°C. In this solution, a mixture solution composed of a monomer inaccordance with a formulation (parts by mass) in Table 3 and 1 part bymass of t-butylperoxy-2-ethylhexanoate was dropped at a constantvelocity for 3 hours. After dropping ended, the temperature of themixture solution was kept for 30 minutes. Thereafter, a mixture solutioncomposed of 30 parts by mass of xylene, 10 parts by mass of n-butanol,and 0.2 part by mass of t-butylperoxy-2-ethylhexanoate was dropped at aconstant velocity for 30 minutes. After dropping ended, the temperatureof the mixture solution was kept for 1 hour. A varnish D was thusobtained. A solid content in obtained varnish D was 50.5 mass % andviscosity was 7 poises. In addition, a number average molecular weightof the resin contained in varnish D was 8000 and an acid value was 70mgKOH/g.

Then, reaction was caused as in Producing Example S21 above except thatin a similar reaction vessel, 100 parts by mass of varnish D, 12.9 partsby mass of copper acetate, 21.9 parts by mass of WW rosin (WW rosin,acid value of 160 mgKOH/g, manufactured by Arakawa Chemical Industries,Ltd.), and 60 parts by mass of xylene were added. Then, a hydrolyzableresin composition S22 having a solid content of 52.5 mass % wasobtained.

Producing Example S23 Preparation of Hydrolyzable Resin Composition S23

In a reaction vessel as in Producing Example S19 above, 70 parts by massof xylol and 20 parts by mass of n-butanol were added and kept at 110°C. In this solution, a mixture solution composed of a monomer inaccordance with a formulation (parts by mass) in Table 3 and 2 parts bymass of t-butylperoxy-2-ethylhexanoate was dropped at a constantvelocity for 3 hours. After dropping ended, the temperature of themixture solution was kept for 1 hour. Thereafter, 10 parts by mass ofxylol were added to thereby obtain a varnish E. A solid content inobtained varnish E was 49.8 mass % and viscosity was 6 poises. Inaddition, a number average molecular weight of the resin contained invarnish E was 8000 and an acid value was 30 mgKOH/g.

Then, in a similar reaction vessel, 100 parts by mass of varnish E, 5.9parts by mass of zinc acetate, 7.5 parts by mass of naphthenic acid(NA-200, acid value of 200 mgKOH/g, manufactured by Daiwa Yushi Kogyo),and 60 parts by mass of xylene were added, a temperature of the mixturewas raised to a reflux temperature, and reaction was continued for 18hours while a distilled mixture solution of acetic acid, water, and asolvent was removed and a xylol/n-butanol mixture solution in the sameamount was replenished. An end point of reaction was determined byquantifying an amount of acetic acid in the distilled solvent. After thereaction solution was cooled, n-butanol and xylene were added to therebyobtain a hydrolyzable resin composition S23 having a solid content of53.8 mass %.

Producing Example S24 Preparation of Hydrolyzable Resin Composition S24

In a reaction vessel as in Producing Example S19 above, 40 parts by massof xylol and 40 parts by mass of n-butanol were added and kept at 110°C. In this solution, a mixture solution composed of a monomer inaccordance with a formulation (parts by mass) in Table 3 and 2 parts bymass of t-butylperoxy-2-ethylhexanoate was dropped at a constantvelocity for 3 hours. After dropping ended, the temperature of themixture solution was kept for 1 hour. Thereafter, a mixture solutioncomposed of 10 parts by mass of xylene, 10 parts by mass of n-butanol,and 0.2 part by mass of t-butylperoxy-2-ethylhexanoate was dropped at aconstant velocity for 30 minutes. After dropping ended, the temperatureof the mixture solution was kept for 1 hour. A varnish F was thusobtained. A solid content in obtained varnish F was 50.0 mass andviscosity was 11 poises. In addition, a number average molecular weightof the resin contained in varnish F was 8000 and an acid value was 130mgKOH/g.

Then, reaction was caused as in Producing Example S23 above except thatin a similar reaction vessel, 100 parts by mass of varnish F, 23.1 partsby mass of zinc acetate, 39.4 parts by mass of naphthenic acid (NA-165,acid value of 165 mgKOH/g, manufactured by Daiwa Yushi Kogyo), and 60parts by mass of xylene were added. Then, a hydrolyzable resincomposition S24 having a solid content of 47.3 mass % was obtained.

Producing Example S25 Preparation of Hydrolyzable Resin Composition S25

In a reaction vessel as in Producing Example S19 above, 70 parts by massof xylol and 30 parts by mass of n-butanol were added and kept at 105°C. In this solution, a mixture solution composed of a monomer inaccordance with a formulation (parts by mass) in Table 3 and 2 parts bymass of azobisisobutyronitrile was dropped at a constant velocity for 3hours. After dropping ended, the temperature of the mixture solution waskept for 1 hour. A varnish G was thus obtained. A solid content inobtained varnish G was 50.0 mass % and viscosity was 18 poises. Inaddition, a number average molecular weight of the resin contained invarnish G was 15000 and an acid value was 50 mgKOH/g.

Then, reaction was caused as in Producing Example S21 above except thatin a similar reaction vessel, 100 parts by mass of varnish G, 9.3 partsby mass of copper acetate, 12.5 parts by mass of naphthenic acid(NA-200, acid value of 200 mgKOH/g, manufactured by Daiwa Yushi Kogyo),and 60 parts by mass of xylene were added. Then, a hydrolyzable resincomposition S25 having a solid content of 51.8 mass % was obtained.

Producing Example S26 Preparation of Hydrolyzable Resin Composition S26

In a reaction vessel as in Producing Example S19 above, 90 parts by massof xylol were added and kept at 105° C. In this solution, a mixturesolution composed of a monomer in accordance with a formulation (partsby mass) in Table 3 and 3 parts by mass oft-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 3hours. After dropping ended, the temperature of the mixture solution waskept for 30 minutes. Thereafter, a mixture solution composed of 10 partsby mass of xylene, 10 parts by mass of n-butanol, and 0.2 part by massof t-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for30 minutes. After dropping ended, the temperature of the mixturesolution was kept for 1.5 hours. A varnish H was thus obtained. A solidcontent in obtained varnish H was 50.8 mass % and viscosity was 10poises. In addition, a number average molecular weight of the resincontained in varnish H was 12000 and an acid value was 30 mgKOH/g.

Then, reaction was caused as in Producing Example S21 above except thatin a similar reaction vessel, 100 parts by mass of varnish H, 5.6 partsby mass of copper acetate, 9.4 parts by mass of hydrogenated rosin(Hypale CH, acid value of 160 mgKOH/g, manufactured by Arakawa ChemicalIndustries, Ltd.), and 60 parts by mass of xylene were added, and ahydrolyzable resin composition S26 having a solid content of 55.1 mass %was obtained.

Producing Example S27 Preparation of Hydrolyzable Resin Composition S27

In a reaction vessel as in Producing Example S19 above, 64 parts by massof xylol and 16 parts by mass of n-butanol were added and kept at 115°C. In this solution, a mixture solution composed of a monomer inaccordance with a formulation (parts by mass) in Table 3 and 2 parts bymass of t-butylperoxy-2-ethylhexanoate was dropped at a constantvelocity for 3 hours. After dropping ended, the temperature of themixture solution was kept for 1 hour. Thereafter, a mixture solutioncomposed of 16 parts by mass of xylene, 4 parts by mass of n-butanol,and 0.2 part by mass of t-butylperoxy-2-ethylhexanoate was dropped at aconstant velocity for 30 minutes. After dropping ended, the temperatureof the mixture solution was kept for 1 hour. A varnish I was thusobtained. A solid content in obtained varnish I was 49.5 mass % andviscosity was 12 poises. In addition, a number average molecular weightof the resin contained in varnish I was 10000 and an acid value was 110mgKOH/g.

Then, reaction was caused as in Producing Example S23 above except thatin a similar reaction vessel, 100 parts by mass of varnish I, 21.5 partsby mass of zinc acetate, 33.3 parts by mass of naphthenic acid (NA-165,acid value of 165 mgKOH/g, manufactured by Daiwa Yushi Kogyo), and 60parts by mass of xylene were added, and a hydrolyzable resin compositionS27 having a solid content of 45.6 mass % was obtained.

Table 3 summarizes an amount of use of a monomer used for preparation ofvarnishes A to I (a charging amount), and a solid content and viscosityof the varnishes.

TABLE 3 Producing Example S19 S20 S21 S22 S23 S24 S25 S26 S27 Varnish AB C D E F G H I Charging (a) (a1) FM-0711 30.0 20.0 20.0 10.0 AmountFM-0721 20.0 10.0 10.0 (Parts by X-22-174DX 20.0 10.0 Mass) (a2) TM-070110.0 X-22-2404 15.0 (a3) FM-7711 5.0 FM-7721 10.0 X-22-164A 5.0X-22-164C 10.0 (a4) Silicon- 5.0 Containing Monomer H AA 9.0 9.0 3.916.7 6.4 3.9 14.2 (c) TIPSA 20.0 45.0 20.0 20.0 45.0 5.0 30.0 45.0 10.0(d) MMA 45.0 20.0 10.0 25.0 21.1 13.3 8.6 26.1 23.5 EA 15.0 16.0 40.010.0 22.3 EHMA 10.0 CHMA 15.0 6.0 M90G 10.0 15.0 15.0 5.0 15.0 Viscosity(poise) 27 15 10 7 6 11 18 10 12 Solid Content (Mass %) 50.1 49.7 51.250.5 49.8 50.0 50.0 50.8 49.5 A B C D E F G H I Varnish 100 100 100 100100 100 100 100 100 Charging Copper Acetate 12.9 12.9 9.3 5.6 AmountZinc Acetate 5.9 23.1 21.5 (Parts by Hydrogenated Rosin 21.9 9.4 Mass)WW Rosin 21.9 Naphthenic Acid 7.5 39.4 12.5 33.3 Solid Content (Mass %)50.1 49.7 50.6 52.5 53.8 47.3 51.8 55.1 45.6

A trade name and abbreviation shown in Table 3 are as follows (a tradename and abbreviation other than those shown below are as in Tables 1and 2).

(1) X-22-174DX (a trade name, a product of Shin-Etsu Chemical Co.,Ltd.): a silicon-containing polymerizable monomer having m=0, b=3, R¹ toR⁴ and R³¹ each being a methyl group, and R⁵ being a methyl group or ann-butyl group in the general formula (I′) above (a functional groupequivalent of 4600 g/mol)

(2) X-22-2404 (a trade name, a product of Shin-Etsu Chemical Co., Ltd.):a silicon-containing polymerizable monomer having p=0, d=3, and R⁶ to R⁸and R³² each being a methyl group in the general formula (II′) above (afunctional group equivalent of 420 g/mol)

(3) X-22-164A (a trade name, a product of Shin-Etsu Chemical Co., Ltd.):a silicon-containing polymerizable monomer having q and s=0, f and g=3,and R⁹ to R¹², R³³, and R³⁴ each being a methyl group in the generalformula (III′) above (a functional group equivalent of 860 g/mol)

(4) X-22-164C (a trade name, a product of Shin-Etsu Chemical Co., Ltd.):a silicon-containing polymerizable monomer having q and s=0, f and g=3,and R⁹ to R¹², R³³, and R³⁴ each being a methyl group in the generalformula (In above (a functional group equivalent of 2370 g/mol)

(5) A silicon-containing monomer H: a silicon-containing polymerizablemonomer having t and u=0, j and k=3, v and w=3, and R¹³ to R²², R³⁵, andR³⁶ each being a methyl group in the general formula (IV′) above (thismonomer was commercially available from Nippon Unicar Co., Ltd. under atrade name “F2-312-01”)

(6) AA: acrylic acid

(7) TIPSA: triisopropylsilyl acrylate

(8) EHMA: 2-ethylhexyl methacrylate

(9) CHMA: cyclohexyl methacrylate

(10) M-90G: methoxypolyethyleneglycol methacrylate (NK ester M-90G,manufactured by Shin-Nakamura Chemical Co., Ltd.)

[4] Preparation of Resin Composition for Comparison

Producing Example T1 Preparation of Resin Composition T1

In a four-neck flask including a cooler, a thermometer, a droppingfunnel, and a stirrer, 15 parts by mass of PGM and 70 parts by mass ofxylene were loaded, and a temperature thereof was raised to 110° C.while they were stirred. Then, a mixture composed of 42.1 parts by massof methyl methacylate, 17.9 parts by mass of ethyl acrylate, 10 parts bymass of “FM-7711” (manufactured by Chisso Corporation), 30 parts by massof “FM-0711” (manufactured by Chisso Corporation), 10 parts by mass ofxylene, 11.9 parts by mass of PGM, 3 parts by mass of the chain transferagent α-methylstyrene dimer), 2.5 parts by mass of AIBN, and 7 parts bymass of AMBN was dropped at a constant velocity in 6 hours from thedropping funnel. After dropping ended, 0.5 part by mass of t-butylperoctoate and 10 parts by mass of xylene were dropped in 30 minutesfollowed by further stirring for 1 hour and 30 minutes. Thereafter, 5.1parts by mass of xylene were added to thereby obtain a resin compositionT1. A solid content in resin composition T1 was 45.5 mass % and Gardnerviscosity was +E.

Obtained resin composition T1 was analyzed with GPC (“HLC-8220GPC”manufactured by Tosoh Corporation, eluant: dimethylformamide). Then, avalue for a weight-average molecular weight of the resin contained inresin composition T1 was 8600 in terms of polystyrene.

Producing Example T2 Preparation of Resin Composition T2

In a four-neck flask including a stirrer, a cooler, a temperaturecontrol device, a nitrogen introduction pipe, and a dropping funnel, 64parts by mass of xylene and 16 parts by mass of n-butanol were added,and a temperature thereof was kept at 100° C. In this solution, amixture solution composed of 58.3 parts by mass of ethyl acrylate (EA),15 parts by mass of cyclohexyl methacrylate (CHMA), 10 parts by mass ofmethoxypolyethyleneglycol methacrylate (M-90G), 16.7 parts by mass ofacrylic acid (AA), and 2 parts by mass of t-butylperoxy-2-ethylhexanoate(“Kayaester O” manufactured by Kayaku Akzo Co., Ltd.) was dropped at aconstant velocity in 3 hours. After dropping ended, the temperaturethereof was kept for 30 minutes. Thereafter, a mixture solution composedof 16 parts by mass of xylene, 4 parts by mass of n-butanol, and 0.2part by mass of t-butylperoxy-2-ethylhexanoate (“Kayaester 0”manufactured by Kayaku Akzo Co., Ltd.) was dropped for 30 minutes. Afterdropping ended, the temperature thereof was kept for 1 hour and 30minutes, to thereby obtain a resin varnish. A solid content in theobtained resin varnish was 49.8 mass % and an acid value of the resin inthe resin varnish was 130.

Then, in a similar reaction vessel, 100 parts by mass of the resinvarnish above, 25.4 parts by mass of zinc acetate, 39.2 parts by mass ofnaphthenic acid (NA-165, acid value of 165 mgKOH/g, manufactured byDaiwa Yushi Kogyo), and 110 parts by mass of xylene were added, and themixture was heated to 130° C. to thereby remove acetic acid togetherwith the solvent. Thus, a resin composition T2 having a solid content of41.5 mass % and Gardner viscosity W-X was obtained.

Obtained resin composition T2 was analyzed with GPC (“HLC-8220GPC”manufactured by Tosoh Corporation, eluant: dimethylformamide). Then, avalue for a weight-average molecular weight of the resin contained inresin composition T2 was 8000 in terms of polystyrene.

Producing Example T3 Preparation of Resin Composition T3

In a four-neck flask including a stirrer, a cooler, a temperaturecontrol device, a nitrogen introduction pipe, and a dropping funnel, 64parts by mass of xylene and 16 parts by mass of n-butanol were added,and a temperature thereof was kept at 115° C. In this solution, amixture solution composed of 11.17 parts by mass of methyl methacrylate(MMA), 16.3 parts by mass of ethyl acrylate (EA), 15 parts by mass ofcyclohexyl methacrylate (CHMA), 15 parts by mass of cyclohexyl acrylate(CHA), 30 parts by mass of methoxypolyethyleneglycol methacrylate(M-90G), 10.27 parts by mass of acrylic acid (AA), 12.26 parts by massof methacrylic acid (MAA), and 3 parts by mass oft-butylperoxy-2-ethylhexanoate (“Kayaester 0” manufactured by KayakuAkzo Co., Ltd.) was dropped at a constant velocity for 3 hours. Afterdropping ended, the temperature thereof was kept for 30 minutes.Thereafter, a mixture solution composed of 16 parts by mass of xylene, 4parts by mass of n-butanol, and 0.2 part by mass oft-butylperoxy-2-ethylhexanoate (“Kayaester 0” manufactured by KayakuAkzo Co., Ltd.) was dropped at a constant velocity for 30 minutes. Afterdropping ended, the temperature thereof was kept for 1 hour and 30minutes, to thereby obtain a resin varnish. A solid content in theobtained resin varnish was 49.7 mass % and an acid value of the resin inthe resin varnish was 160.

Then, reaction was caused as in Producing Example T2 above except thatin a similar reaction vessel, 100 parts by mass of the resin varnishabove, 29.6 parts by mass of copper acetate, and 14.5 parts by mass ofpivalic acid (acid value: 550 mgKOH/g) were added. Thus, a resincomposition T3 having a solid content of 45.2 mass % and Gardnerviscosity Z2-Z3 was obtained.

Obtained resin composition T3 was analyzed with GPC (“HLC-8220GPC”manufactured by Tosoh Corporation, eluant: dimethylformamide). Then, avalue for a weight-average molecular weight of the resin contained inresin composition T3 was 6500 in terms of polystyrene.

Producing Example T4 Preparation of Resin Composition T4

In a reaction vessel as in Producing Example S19 above, 80 parts by massof xylol were added and kept at 100° C. In this solution, a mixturesolution composed of 65.0 parts by mass of triisopropylsilyl acrylate(TIPSA), 35.0 parts by mass of methyl methacrylate (MMA), and 2 parts bymass of t-butylperoxy-2-ethylhexanoate was dropped at a constantvelocity for 3 hours. After dropping ended, the temperature of themixture solution was kept for 1 hour. Thereafter, a mixture solutioncomposed of 20 parts by mass of xylene and 0.2 part by mass oft-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 30minutes. After dropping ended, the temperature of the mixture solutionwas kept for 1.5 hours. A resin composition T4 was thus obtained. Asolid content in obtained resin composition T4 was 50.0 mass % andviscosity was 8 poises. In addition, a number average molecular weightof the resin contained in resin composition T4 was 10000.

Producing Example T5 Preparation of Resin Composition T5

In a reaction vessel as in Producing Example S19 above, 64 parts by massof xylol and 16 parts by mass of n-butanol were added and kept at 115°C. In this solution, a mixture solution composed of 40.0 parts by massof triisopropylsilyl acrylate (TIPSA), 9.0 parts by mass of acrylic acid(AA), 26.0 parts by mass of ethyl acrylate (EA), 15.0 parts by mass ofcyclohexyl methacrylate (CHMA), 10.0 parts by mass ofmethoxypolyethyleneglycol methacrylate (M-90G), and 2 parts by mass oft-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 3hours. After dropping ended, the temperature of the mixture solution waskept for 30 minutes. Thereafter, a mixture solution composed of 16 partsby mass of xylene, 4 parts by mass of n-butanol, and 0.2 part by mass oft-butylperoxy-2-ethylhexanoate was dropped at a constant velocity for 30minutes. After dropping ended, the temperature of the mixture solutionwas kept for 1 hour. A resin varnish was thus obtained. A solid contentin the obtained resin varnish was 49.7 mass % and viscosity was 5poises. In addition, a number average molecular weight of the resincontained in this resin varnish was 6000 and an acid value was 70mgKOH/g.

Then, reaction was caused as in Producing Example S21 above except thatin a similar reaction vessel, 100 parts by mass of the resin varnishabove, 12.9 parts by mass of copper acetate, 21.9 parts by mass ofhydrogenated rosin (Hypale CH, acid value of 160 mgKOH/g, manufacturedby Arakawa Chemical Industries, Ltd.), and 60 parts by mass of xylenewere added, and a resin composition T5 having a solid content of 51.3mass % was obtained.

[5] Evaluation of Hiding Performance of Hydrolyzable Resin CompositionsS1 to S27 and Resin Compositions T1 to T5

Obtained hydrolyzable resin compositions S1 to S27 or resin compositionsT1 to T5 were applied with an applicator onto a plate for measuring acontrast ratio in conformity with JIS K 5600-4-1 4.1.2, of 120 mm wide x120 mm high x 0.3 mm thick so that a dry film thickness of a coatingfilm is 150 μm, and left for one day and night in a room for drying, tothereby obtain a test plate having an antifouling coating film. Hidingperformance of a coating film was visually evaluated in accordance withthe following criteria, for the obtained test plates:

A Completely seen through; a boundary between white and black on theplate for measuring a contrast ratio can readily be identified;

B Slightly seen through; a boundary between white and black on the platefor measuring a contrast ratio can be identified to some degree; and

C Completely hidden; a boundary between white and black on the plate formeasuring a contrast ratio cannot be identified.

As a result of the hiding performance evaluation test above, it wasconfirmed that coating films formed from hydrolyzable resin compositionsS1 to S27 and resin compositions T1 to T5 were each high in transparencyand the resin itself did not have a hiding performance.

Examples 1 to 13 Comparative Examples 1 to 2

[6] Preparation of Colored Antifouling Paint

By mixing each formulated component with a high-speed disperser inaccordance with a formulation (parts by mass) in Table 4, coloredantifouling paints (paints 1 to 15) were prepared. It is noted thatpaint 3 according to Example 3 was prepared by mixing paints 1 and 2 ata blending ratio shown in Table 4.

TABLE 4 Example 1 2 3 4 5 6 7 8 9 Paint No. 1 2 3 4 5 6 7 8 9Hydrolyzable S2 93.85 94.16 Resin S4 82.22 Composition S7 or Resin S1380.94 Composition S16 91.97 S19 90.41 S20 S21 93.72 S23 93.25 S25 S27 T4T5 Cuprous Oxide 1.20 Antifouling Agent 1 0.75 Antifouling Agent 2Antifouling Agent 3 3.54 Antifouling Agent 4 4.85 Antifouling Agent 53.69 2.21 2.17 Titanium Oxide 0.25 0.16 0.31 0.17 0.68 0.20 0.10Azo-Based Yellow Pigment Azo-Based Red Pigment 0.71 0.48 0.60 0.23 0.450.51 Phthalocyanine Blue 0.82 0.51 Carbon Black Thermoplastic Resin 12.37 2.37 Thermoplastic Resin 2 7.06 Thermoplastic Resin 3 2.28Thermoplastic Resin 4 1.28 Plasticizer 1 3.02 Plasticizer 2 Plasticizer3 2.35 Plasticizer 4 11.29 Barium Sulfate Anti-Settling Agent 2.82 2.832.72 2.80 2.82 2.47 3.21 3.21 Xylene Paint 1 28.57 Paint 2 71.43 Total100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 ColorTone of Paint Red Pink Blue L*/a*/b* of Coating Film 35/63/18 34/63/1713/5/−1 11/6/5 40/60/13 17/15/−55 18/12/−52 Target Dry Film 50 150 125125 125 125 125 125 125 Thickness T (μm) Comparative Example Example 1011 12 13 1 2 Paint No. 10 11 12 13 14 15 Hydrolyzable S2 Resin S4Composition S7 80.60 or Resin S13 Composition S16 S19 S20 92.37 S21 S23S25 91.85 S27 82.62 T4 52.25 T5 34.34 Cuprous Oxide 6.27 35.35Antifouling Agent 1 0.72 Antifouling Agent 2 0.93 4.04 Antifouling Agent3 6.88 Antifouling Agent 4 10.84 Antifouling Agent 5 Titanium Oxide 0.300.78 10.10 2.02 Azo-Based Yellow 0.89 Pigment Azo-Based Red Pigment 0.030.64 3.03 Phthalocyanine Blue 0.49 Carbon Black 0.09 Thermoplastic Resin1 5.05 Thermoplastic Resin 2 2.16 Thermoplastic Resin 3 3.55 3.03Thermoplastic Resin 4 Plasticizer 1 4.01 Plasticizer 2 2.96 2.16Plasticizer 3 Plasticizer 4 3.27 Barium Sulfate 5.31 Anti-Settling Agent3.45 3.47 3.37 3.01 3.13 3.03 Xylene 21.51 10.10 Paint 1 Paint 2 Total100.00 100.00 100.00 100.00 100.00 100.00 Color Tone of Paint BlueYellow Gray White Red L*/a*/b* of Coating Film 17/0/−26 80/1/51 34/0/−397/0/1 33/23/10 32/49/16 Target Dry Film 125 125 125 125 125 125Thickness T (μm) Unit: Parts by Mass Details of each component shown inTable 4 are as follows. (1) Cuprous oxide: “NC-301” manufactured by NCTech (2) Antifouling agent 1: ZPT (zinc pyrithione) (“ZincOMADINE”manufactured by Arch Chemicals) (3) Antifouling agent 2: CuPT(copper pyrithione) “Copper OMADINE” manufactured by Arch Chemicals) (4)Antifouling agent 3:1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfenamide(“Preventol A5S” manufactured by Lanxess) (5) Antifouling agent 4:4,5-dichloro-2-n-octyl-4-isothiazoline-3-one(4,5-dichloro-2-noctyl-3(2H)isothiazolone) (“SeaNine 211” manufactured by Rohm and HaasCompany) (6) Antifouling agent 5:4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile(“ECONEA” manufactured by Janssen PMP) (7) Titanium oxide: “TI-PURER-900” manufactured by Du Pont Kabushiki Kaisha (8) Azo-based yellowpigment: “Seika Fast Yellow 2054C” manufactured by Dainichiseika Color &Chemicals Mfg. Co., Ltd. (9) Azo-based red pigment: “FUJI FAST RED2305A” manufactured by Fuji Pigment Co., Ltd. (10) Phthalocyanine blue:“CYANINE BLUE G-105” manufactured by Sanyo Color Works, Ltd. (11) CarbonBlack: “SUNBLACK X15” manufactured by Asahi Carbon Co., Ltd. (12)Thermoplastic resin 1: Chlorinated paraffin (“Toyoparax A50”manufactured by Tosoh Corporation) (13) Thermoplastic resin 2: Polyvinylether (“Lutonal A25” manufactured by BASF JAPAN) (14) Thermoplasticresin 3: Rosin (“WW Rosin” manufactured by Arakawa Chemical Industries,Ltd.) (15) Thermoplastic resin 4: Vinyl chloride-isobutyl vinyl ethercopolymer (“Laroflex MP25” manufactured by BASF JAPAN) (16) Plasticizer1: DOP (dioctyl phthalate) (“DOP” manufactured by Mitsubishi GasChemical Company, Inc.) (17) Plasticizer 2: DIDP (diisodecyl phthalate)(“DIDP” manufactured by Chisso Corporation) (18) Plasticizer 3: TCP(tricresyl phosphate) (“TCP” manufactured by Daihachi Chemical IndustryCo., Ltd.) (19) Plasticizer 4: Triaryl phosphate (“Rheophos 65”manufactured by Ajinomoto Co., Inc.) (20) Barium sulfate: “Barite PowderFBA” manufactured by Naigai Talc. Co., Ltd. (21) Anti-settling agent:“Disparlon A600-20X” manufactured by Kusumoto Chemicals, Ltd.

[7] Formation of Antifouling Coating Film Using Paints 1 to 15 andEvaluation of Film Thickness Determination Function of Paints 1 to 15

Any of paints a to 1 serving as an undercoat paint was applied to ablast plate, to which a rustproof paint had been applied in advance,until a surface of the blast plate was completely hidden, and the blastplate was left for 2 days and nights for drying. A test plate having anundercoat coating film was thus obtained. Details of undercoat paints ato 1 are as follows (with a color tone in accordance with the L*/a*/b*color system of each undercoat paint being shown in parentheses). Tables5 to 8 show a color tone of a surface of the undercoat coating film ofthe test plate.

(a) Paint a: Antifouling paint “Ecoloflex SPC250 HyB Cherry V”manufactured by Nippon Paint Marine Coatings Co., Ltd.(L*/a*/b*=31/23/8)

(b) Paint b: Antifouling paint “Ecoloflex SPC200 Red Brown” manufacturedby Nippon Paint Marine Coatings Co., Ltd. (L*/a*/b*=32/17/6)

(c) Paint c: Antifouling paint “Unagi Toryo Ichiban Azayaka Tokujou RedA” manufactured by Nippon Paint Marine Coatings Co., Ltd.(L*/a*/b*=36/50/13)

(d) Paint d: Anti-corrosive paint “Uniprime 100 Red Oxide” manufacturedby Nippon Paint Marine Coatings Co., Ltd. (L*/a*/b*=27/27/15)

(e) Paint e: Antifouling paint “Ecoloflex SPC150 HyB Brown” manufacturedby Nippon Paint Marine Coatings Co., Ltd. (L*/a*/b*=33/21/10)

(f) Paint f: Anti-corrosive paint “Nippon R-Marine A/C Light Brown”manufactured by Nippon Paint Marine Coatings Co., Ltd. (L*/a*/b*=54/6/4)

(g) Paint g: Antifouling paint “Hisol 100 Blue A” manufactured by NipponPaint Marine Coatings Co., Ltd. (L*/a*/b*=31/7/−43)

(h) Paint h: Antifouling paint “Ecoloflex SPC Beatle Black” manufacturedby Nippon Paint Marine Coatings Co., Ltd. (L*/a*/b*=21/0/−1)

(i) Paint i: Anti-corrosive paint “Nippon V-Marine A/C TF Silver”manufactured by Nippon Paint Marine Coatings Co., Ltd.(L*/a*/b*=58/−1/−1)

(j) Paint j: Anti-corrosive paint “NOA A/C II Gray” manufactured byNippon Paint Marine Coatings Co., Ltd. (L*/a*/b*=60/−1/0)

(k) Paint k: Anti-corrosive paint “NOA 10F Buff 250” manufactured byNippon Paint Marine Coatings Co., Ltd. (L*/a*/b*=60/1/31)

(l) Paint 1: Anti-corrosive paint “Nippon E-Marine Primer Galva White”manufactured by Nippon Paint Marine Coatings Co., Ltd.(L*/a*/b*=87/−1/3)

Then, the surface of the undercoat coating film on the obtained testplate having the undercoat coating film was painted with airlessspraying, with a colored antifouling paint (any of paints 1 to 15)serving as a topcoat paint obtained in each of Examples and ComparativeExamples, and the test plate was left in a room for 2 days and nightsfor drying. The antifouling coating films each having the dry filmthickness shown in Tables 5 to 8 were thus formed. Each film thicknessof the dry coating film of the topcoat paint was 25, 40, 50, and 60 μmin Example 1, 25, 50, 75, 100, 125, 150, and 180 μm in Example 2, and25, 50, 75, 100, 125, and 150 μm in Examples 3 to 13 and ComparativeExamples 1 to 2. The dry film thickness was measured with “MiniTest3100” (manufactured by ElektroPhysik).

With regard to the obtained topcoat antifouling coating film having eachdry film thickness, a color difference ΔE between the topcoatantifouling coating film having each dry film thickness and the topcoatantifouling coating film having a target dry film thickness T of eachpaint (the target dry film thickness T of each paint being as shown inTable 4 and Tables 5 to 8) was obtained by measurement with atristimulus colorimeter SM color meter (model number SM-T45 manufacturedby Suga Test Instruments Co., Ltd., JIS 28722) in conformity with JIS K5600-4-5 and by calculation in conformity with JIS K 5600-4-6. Inaddition, an ability for the topcoat antifouling coating film havingeach dry film thickness to hide an underlying substrate (an ability forthe topcoat antifouling coating film to hide the undercoat coating film)was visually observed and evaluated based on the criteria below. Tables5 to 8 also show the results.

A: Entirely seen through

B: Very noticeably seen through

C: Noticeably seen through

D: Substantially hidden, but slightly seen through

E: Completely hidden

It is noted that ΔE at dry film thickness of 0 μm in Tables 5 to 8indicates color difference ΔE3 between each paint and the surface of theundercoat coating film. In addition, “color tone of coating film” in thefield of the undercoat paint represents a color tone of the surface ofthe undercoat coating film, not the color tone of the undercoat paintitself.

TABLE 5 Example 1 Topcoat Paint Paint No. Paint 1 Color Tone of RedCoating film Target Dry 50 μm Film Thickness Undercoat Paint Paint No.Paint c Color Tone of Red Coating film Dry Film Hiding Thickness ΔEAbility Color Difference ΔE 0 μm 14.0 — from Topcoat 25 μm 6.2 BAntifouling Coating Film 40 μm 2.4 C Having Target Dry Film 50 μm 0.0 EThickness 60 μm 0.2 E

TABLE 6 Example 2 Topcoat Paint Paint No. Paint 2 Color Tone of RedCoating film Target Dry 150 μm Film Thickness Undercoat Paint Paint No.Paint j Color Tone of Coating film Gray Dry Film Hiding Thickness ΔEAbility Color Difference ΔE 0 μm 71.0 — from Topcoat 25 μm 35.0 AAntifouling Coating Film 50 μm 17.0 A Having Target Dry Film 75 μm 8.3 BThickness 100 μm 4.1 B 125 μm 2.1 C 150 μm 0.0 E 180 μm 0.2 E

TABLE 7 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8Topcoat Paint Paint No. Paint 3 Paint 4 Paint 5 Paint 6 Paint 7 Paint 8Color Tone of Red Red Red Red Pink Blue Coating Film Target Dry Film 125μm 125 μm 125 μm 125 μm 125 μm 125 μm Thickness Undercoat Paint PaintNo. Paint k Paint d Paint f Paint c Paint i Paint h Color Tone of BuffRed Oxide Brown Red Silver Black Coating Film Dry Film Hiding HidingHiding Hiding Hiding Hiding Thickness ΔE Ability ΔE Ability ΔE AbilityΔE Ability ΔE Ability ΔE Ability Color Difference 0 μm 71.0 — 36.0 —42.0 — 51.0 — 67.0 — 56.0 — ΔE from Topcoat 25 μm 34.0 A 21.0 A 25.0 A28.0 A 30.1 A 28.7 A Antifouling Coating 50 μm 16.5 A 11.0 A 13.0 A 14.5A 15.0 A 14.4 A Film Having Target 75 μm 7.4 B 5.1 B 6.1 B 6.5 B 6.9 B6.7 B Dry Film Thickness 100 μm 2.7 C 2.3 C 2.4 C 2.5 C 2.4 C 2.4 C 125μm 0.0 E 0.0 E 0.0 E 0.0 E 0.0 E 0.0 E 150 μm 0.2 E 0.2 E 0.3 E 0.4 E0.3 E 0.4 E Example 9 Example 10 Example 11 Example 12 Example 13Topcoat Paint Paint No. Paint 9 Paint 10 Paint 11 Paint 12 Paint 13Color Tone of Blue Blue Yellow Gray White Coating Film Target Dry Film125 μm 125 μm 125 μm 125 μm 125 μm Thickness Undercoat Paint Paint No.Paint e Paint b Paint a Paint l Paint g Color Tone of Brown Red BrownWhite Blue Coating Film Dry Film Hiding Hiding Hiding Hiding HidingThickness ΔE Ability ΔE Ability ΔE Ability ΔE Ability ΔE Ability ColorDifference 0 μm 64.0 — 39.0 — 69.0 — 54.0 — 80.0 — ΔE from Topcoat 25 μm29.4 A 23.0 A 32.2 A 26.7 A 36.0 A Antifouling Coating 50 μm 14.4 A 12.4A 15.7 A 13.2 A 17.4 A Film Having Target 75 μm 6.6 B 5.7 B 7.2 B 6.2 B8.1 B Dry Film Thickness 100 μm 2.3 C 2.2 C 2.6 C 2.3 C 2.5 C 125 μm 0.0E 0.0 E 0.0 E 0.0 E 0.0 E 150 μm 0.3 E 0.4 E 0.3 E 0.4 E 0.4 E

TABLE 8 Comparative Comparative Example 1 Example 2 Topcoat Paint PaintNo. Paint 14 Paint 15 Color Tone of Red Red Coating Film Target Dry Film125 μm 125 μm Thickness Undercoat Paint Paint No. Paint i Paint b ColorTone of Silver Red Coating Film Dry Film Hiding Hiding Thickness ΔEAbility ΔE Ability Color Difference 0 μm 36.0 — 35.0 — ΔE from Topcoat25 μm 14.0 A 0.7 E Antifouling Coating 50 μm 5.0 B 0.4 E Film HavingTarget 75 μm 2.5 C 0.2 E Dry Film Thickness 100 μm 1.3 D 0.1 E 125 μm0.0 E 0.0 E 150 μm 0.3 E 0.1 E

Table 9 summarizes ΔE1 of the colored antifouling paints (paints 1 to15) in Examples 1 to 13 and Comparative Examples 1 to 2 (a colordifference between the coating film formed from the colored antifoulingpaint having the target dry film thickness T and the coating film formedfrom the colored antifouling paint having the dry film thickness of 0.8T), ΔE2 thereof (a color difference between the coating film formed fromthe colored antifouling paint having the target dry film thickness T andthe coating film formed from the colored antifouling paint having thedry film thickness of 1.2 T), and color difference ΔE3 thereof (a colordifference between the colored antifouling paint and the undercoatcoating film) calculated based on the results shown in Tables 5 to 8above. In addition, FIG. 1 shows a graph of relation between the dryfilm thickness and ΔE (a color difference between the topcoatantifouling coating film having each dry film thickness and the topcoatantifouling coating film having the target dry film thickness) of paints3 to 15 shown in Tables 7 and 8, and FIG. 2 is a diagram showing a partof FIG. 1 (in the vicinity of the target dry film thickness of 125 μm)in an enlarged view.

TABLE 9 Paint No. ΔE1 ΔE2 ΔE3 Example 1 Paint 1 2.4 0.2 14.0 Example 2Paint 2 2.1 0.2 71.0 Example 3 Paint 3 2.7 0.2 71.0 Example 4 Paint 42.3 0.2 36.0 Example 5 Paint 5 2.4 0.3 42.0 Example 6 Paint 6 2.5 0.451.0 Example 7 Paint 7 2.4 0.3 67.0 Example 8 Paint 8 2.4 0.4 56.0Example 9 Paint 9 2.3 0.3 64.0 Example 10 Paint 10 2.2 0.4 39.0 Example11 Paint 11 2.6 0.3 69.0 Example 12 Paint 12 2.3 0.4 54.0 Example 13Paint 13 2.5 0.4 80.0 Comparative Paint 14 1.3 0.3 36.0 Example 1Comparative Paint 15 0.1 0.1 35.0 Example 2

As shown above, it can be seen that paints 1 to 13 according to Examples1 to 13 are the colored antifouling paints excellent in film thicknessdetermination function satisfying conditions (a) to (b) and (d) above.In particular, since ΔE1 is as great as 2.0 or more, dependence on afilm thickness, of the color tone of the coating film just beforepainting is completed is great, and hence change in hiding performancejust before painting is completed can easily visually be determined.According to the method of forming an antifouling coating film of thepresent invention employing such a colored antifouling paint excellentin film thickness determination function, a dry coating film having atarget dry film thickness can extremely accurately be formed and evensmall shortage in film thickness can be avoided. On the other hand,paint 14 according to Comparative Example 1 has ΔE1 as small as 1.3, andtherefore it is more difficult than paints 1 to 13 to visually determinechange in hiding performance just before painting is completed. Paint 15according to Comparative Example 2 hardly has the film thicknessdetermination function.

Reference Examples 1 to 59 and Comparative Reference Examples 1 to 7

Antifouling paints were prepared by using hydrolyzable resin (i)obtained in Producing Examples S1 to S27 above [hydrolyzable resincompositions S1 to S18] or (ii) [hydrolyzable resin compositions S19 toS27] or resin compositions T1 to 15 obtained in Producing Examples T1 toT5 and other components shown in Tables 10 to 13 in accordance with aformulation (parts by mass) in Tables 10 to 13 and mixing the componentswith a high-speed disperser.

TABLE 10 Reference Example 1 2 3 4 5 6 7 8 9 10 11 Hydrolyzable S1 84.0Resin S2 80.0 63.0 Composition S3 88.5 or Resin S4 73.5 Composition S570.0 S6 88.0 76.5 S7 70.0 S8 85.0 S9 82.3 Cuprous Oxide AntifoulingAgent 1 Antifouling Agent 2 Antifouling Agent 3 Antifouling Agent 4Antifouling Agent 5 Titanium Oxide Yellow Iron Oxide Azo-Based RedPigment Phthalocyanine Blue Thermoplastic Resin 1 16.5 20.0Thermoplastic Resin 2 10.0 20.0 15.0 Thermoplastic Resin 3 6.0 12.0Thermoplastic Resin 4 2.0 Plasticizer 1 5.0 Plasticizer 2 13.5Plasticizer 3 7.7 Plasticizer 4 1.5 Barium Sulfate Anti-Settling AgentXylene 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Total100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 TotalAmount (Parts by 15.6 27.7 3.7 49.9 62.4 5.0 62.7 13.0 20.5 39.0 95.2Mass) of Thermoplastic Resin and Plasticizer with Respect to 100 Partsby Mass of Resin (Solid Content) Reference Example 12 13 14 15 16 17 1819 Hydrolyzable S1 68.0 Resin S2 Composition S3 55.0 or Resin S4 65.061.0 Composition S5 76.5 S6 62.0 S7 78.1 68.0 S8 S9 Cuprous Oxide 3.0Antifouling Agent 1 2.0 3.0 Antifouling Agent 2 2.0 Antifouling Agent 32.0 Antifouling Agent 4 4.5 2.0 Antifouling Agent 5 2.0 2.0 TitaniumOxide 2.0 2.0 2.0 2.0 2.0 Yellow Iron Oxide 1.0 Azo-Based Red Pigment14.0 3.0 4.0 Phthalocyanine Blue 4.0 4.0 Thermoplastic Resin 1 5.3 10.04.0 Thermoplastic Resin 2 10.0 Thermoplastic Resin 3 14.0 8.0Thermoplastic Resin 4 5.0 11.0 Plasticizer 1 12.0 Plasticizer 2 4.6 5.0Plasticizer 3 4.0 8.0 Plasticizer 4 11.0 Barium Sulfate 3.0Anti-Settling Agent 2.0 2.0 2.0 2.0 2.0 Xylene 10.0 10.0 10.0 4.0 12.011.0 12.0 10.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0Total Amount (Parts by 85.5 27.8 25.7 88.5 32.2 58.3 39.2 29.0 Mass) ofThermoplastic Resin and Plasticizer with Respect to 100 Parts by Mass ofResin (Solid Content) Unit: Parts by Mass

TABLE 11 Reference Example 20 21 22 23 24 25 26 27 28 29 30 HydrolyzableS10 85.0 84.0 Resin S11 70.0 63.0 Composition S12 70.0 or Resin S13 88.0Composition S14 80.0 S15 82.3 S16 73.5 S17 76.5 S18 88.5 Cuprous OxideAntifouling Agent 1 Antifouling Agent 2 Antifouling Agent 3 AntifoulingAgent 4 Antifouling Agent 5 Titanium Oxide Yellow Iron Oxide Azo-BasedRed Pigment Phthalocyanine Blue Thermoplastic Resin 1 20.0 16.5Thermoplastic Resin 2 20.0 10.0 15.0 Thermoplastic Resin 3 6.0 12.0Thermoplastic Resin 4 2.0 Plasticizer 1 5.0 Plasticizer 2 13.5Plasticizer 3 7.7 Plasticizer 4 1.5 Barium Sulfate Anti-Settling AgentXylene 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Total100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 TotalAmount (Parts by 12.7 62.0 61.6 5.0 27.4 20.6 49.2 38.7 3.7 15.5 92.8Mass) of Thermoplastic Resin and Plasticizer with Respect to 100 Partsby Mass of Resin (Solid Content) Reference Example 31 32 33 34 35 36 3738 Hydrolyzable S10 61.0 Resin S11 68.0 Composition S12 62.0 or ResinS13 55.0 Composition S14 78.1 68.0 S15 65.0 S16 76.5 S17 S18 CuprousOxide 3.0 Antifouling Agent 1 2.0 3.0 Antifouling Agent 2 2.0Antifouling Agent 3 2.0 Antifouling Agent 4 4.5 2.0 Antifouling Agent 52.0 2.0 Titanium Oxide 2.0 2.0 2.0 2.0 2.0 Yellow Iron Oxide 1.0Azo-Based Red Pigment 14.0 3.0 4.0 Phthalocyanine Blue 4.0 4.0Thermoplastic Resin 1 5.3 10.0 4.0 Thermoplastic Resin 2 10.0Thermoplastic Resin 3 14.0 8.0 Thermoplastic Resin 4 5.0 Plasticizer 112.0 11.0 Plasticizer 2 4.6 5.0 Plasticizer 3 4.0 8.0 Plasticizer 4 11.0Barium Sulfate 3.0 Anti-Settling Agent 2.0 2.0 2.0 2.0 2.0 Xylene 10.010.0 10.0 4.0 12.0 11.0 12.0 10.0 Total 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 Total Amount (Parts by 84.7 27.8 25.8 87.3 31.9 56.838.2 29.0 Mass) of Thermoplastic Resin and Plasticizer with Respect to100 Parts by Mass of Resin (Solid Content) Unit: Parts by Mass

TABLE 12 Reference Example 39 40 41 42 43 44 45 46 47 48 49 50Hydrolyzable S19 84.0 Resin S20 76.5 95.0 Composition S21 88.5 or ResinS22 88.0 Composition S23 82.3 95.0 S24 70.0 S25 70.0 S26 85.0 80.0 S2773.5 Cuprous Oxide Antifouling Agent 1 Antifouling Agent 2 AntifoulingAgent 3 Antifouling Agent 4 Antifouling Agent 5 Titanium Oxide YellowIron Oxide Azo-Based Red Pigment Phthalocyanine Blue Thermoplastic Resin1 20.0 16.5 Thermoplastic Resin 2 20.0 10.0 Thermoplastic Resin 3 6.0Thermoplastic Resin 4 2.0 Plasticizer 1 5.0 Plasticizer 2 13.5Plasticizer 3 7.7 Plasticizer 4 1.5 Barium Sulfate Anti-Settling AgentXylene 10.0 10.0 5.0 10.0 10.0 10.0 5.0 10.0 10.0 10.0 10.0 10.0 Total100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0Total Amount (Parts by 14.3 35.5 0 3.3 4.3 17.4 0 60.4 55.2 10.7 49.222.7 Mass) of Thermoplastic Resin and Plasticizer with Respect to 100Parts by Mass of Resin (Solid Content) Reference Example 51 52 53 54 5556 57 58 59 Hydrolyzable S19 68.0 Resin S20 68.0 Composition S21 78.1 orResin S22 59.5 Composition S23 76.5 S24 55.0 S25 65.0 S26 61.0 S27 62.0Cuprous Oxide 3.0 Antifouling Agent 1 2.0 3.0 Antifouling Agent 2 2.0Antifouling Agent 3 2.0 Antifouling Agent 4 4.5 2.0 Antifouling Agent 52.0 2.0 Titanium Oxide 2.0 2.0 2.0 2.0 2.0 Yellow Iron Oxide 1.0Azo-Based Red Pigment 14.0 3.0 4.0 Phthalocyanine Blue 4.0 4.0Thermoplastic Resin 1 5.3 10.0 4.0 Thermoplastic Resin 2 15.0Thermoplastic Resin 3 15.5 14.0 8.0 Thermoplastic Resin 4 5.0 11.0Plasticizer 1 12.0 Plasticizer 2 4.6 5.0 Plasticizer 3 4.0 10.0 8.0Plasticizer 4 11.0 Barium Sulfate 3.0 Anti-Settling Agent 2.0 2.0 2.02.0 2.0 Xylene 10.0 10.0 10.0 10.0 4.0 12.0 11.0 12.0 10.0 Total 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Total Amount (Parts by97.6 74.3 25.1 21.9 84.6 29.6 47.6 38.9 26.4 Mass) of ThermoplasticResin and Plasticizer with Respect to 100 Parts by Mass of Resin (SolidContent) Unit: Parts by Mass

TABLE 13 Comparative Reference Example 1 2 3 4 5 6 7 Hydrolyz- T1 90.0able T2 62.0 Resin T3 57.0 Composi- T4 85.0 72.0 tion or T5 55.0 69.0Resin Composi- tion Cuprous Oxide 5.0 3.0 Zinc White 4.0 AntifoulingAgent 1 2.0 Antifouling Agent 2 2.0 2.0 2.0 Antifouling Agent 3 2.0 2.0Antifouling Agent 4 2.0 Antifouling Agent 5 Titanium Oxide 3.0 2.0Azo-Based Red 2.0 Pigment Phthalocyanine 2.0 1.0 Blue Red Iron Oxide 4.05.0 6.0 3.0 Thermoplastic 5.0 5.0 15.0 5.0 Resin 1 Thermoplastic Resin 2Thermoplastic 3.0 3.0 3.0 Resin 3 Thermoplastic Resin 4 Plasticizer 15.0 Plasticizer 2 20.0 Plasticizer 3 Plasticizer 4 3.0 3.0 5.0 BariumSulfate Anti-Settling 2.0 2.0 2.0 2.0 Agent Xylene 10.0 11.0 11.0 10.010.0 10.0 11.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 TotalAmount 0 23 25 11.8 124.0 13.9 22.6 (Parts by Mass) of ThermoplasticResin and Plasticizer with Respect to 100 Parts by Mass of Resin (SolidContent) Unit: Parts by Mass

Details of each component shown in Tables 10 to 13 are as follows (atrade name and abbreviation other than those shown below are as in Table4).

(1) Zinc white: “Zinc Oxide Type 2” manufactured by Sakai ChemicalIndustry Co., Ltd.

A long-term antifouling property, adhesiveness with an underlyingsubstrate, resistance to cracking, and a polishing property of theantifouling coating film formed from each obtained antifouling paintabove were evaluated in accordance with the evaluation method below.Tables 14 to 17 show evaluation results.

(1) Long-Term Antifouling Property

The obtained antifouling paint was applied to a blast plate, to which arustproof paint had been applied in advance so that a dry film thicknessof a coating film is 300 μm, and the blast plate was left in a room for2 days and nights for drying. The test plate having the antifoulingcoating film was thus obtained. The obtained test plate was subjected toan organism adhesion test by using an experimental raft installed inMarine Research Laboratory of Nippon Paint Marine Coatings Co., Ltd. inTamano, Okayama Prefecture and an antifouling property was evaluated.The number of months in the table shows a period during which the raftwas immersed. In addition, a numeric value in the table shows a ratio(%) occupied by an area of adhesion of organisms in an area of thecoating film (determination by visual inspection), and a ratio nothigher than 15% was determined as pass.

(2) Adhesiveness with Underlying Substrate (Cross-Cut Adhesion Test)

A test plate A obtained by applying the obtained antifouling paint to ablast plate, to which a rustproof paint had been applied in advance sothat a dry film thickness of a coating film is 150 μm and leaving theblast plate in a room for 2 days and night for drying, and a test plateB obtained by preparing a substrate obtained by immersing test plate Ain sterilized and filtered seawater for three months and thereafterleaving the test plate in a room for 1 day and night for drying,applying to the surface of the coating film on the substrate theantifouling paint the same as that used for formation of the coatingfilm so that a dry film thickness of a coating film is 150 μm, andleaving the substrate in a room for 2 days and nights for drying wereused to conduct a cross-cut adhesion test in conformity with JIS K5600.5.6 (a grid interval of 2 mm and the number of grids of 25). Anumeric value in the table represents the results of the test as a scoredefined under the criteria below.

Evaluation score 10: Each cut is thin, opposing sides of the cut aresmooth, and there is no peel-off at each intersection of cuts and ateach corner of a square.

Evaluation score 8: There is slight peel-off at an intersection of cuts,there is no peel-off at each corner of a square, and an area of amissing portion is within 5% of the total area of a square.

Evaluation score 6: There is peel-off on opposing sides of a cut and atan intersection of the cuts, and an area of a missing portion occupies 5to 15% of the total area of a square.

Evaluation score 4: There is peel-off across a great width due to a cutand an area of a missing portion occupies 15 to 35% of the total area ofa square.

Evaluation score 2: A width of peel-off due to a cut is greater than inthe case of evaluation score 4 and an area of a missing portion occupies35 to 65% of the total area of a square.

Evaluation score 0: An area of peel-off occupies 65% or more of thetotal area of a square.

(3) Resistance to Cracking

(a) Resistance to Cracking Against Immersion in Seawater (Evaluation ofState of Coating Film After Immersion in Seawater)

A state of the coating film on the test plate after 6 months of a raftimmersion period in the long-term antifouling property test above wasobserved visually and with rubbing, and then evaluated. A coating filmin which no crack was observed was evaluated as A and a coating film inwhich a crack was observed was evaluated as B.

(b) Resistance to Cracking Against Repeated Drying and Wetting (Dry andWet Alternating Test)

A test plate having the antifouling coating film was obtained byapplying the obtained antifouling paint to a blast plate, to which arustproof paint had been applied in advance so that a dry film thicknessof a coating film is 300 μm and leaving the blast plate in a room for 2days and nights for drying. The obtained test plate was immersed for 1week in seawater at 40° C. followed by drying in a room for 1 week, anda dry and wet alternating test with this procedure being defined as 1cycle was conducted 20 cycles at the maximum. If a crack is generated inthe coating film during the test, the test was terminated at the timepoint of generation of a crack and the number of cycles at that timepoint is shown in the table. A plate having no crack after 20 cycles wasevaluated as A.

(4) Polishing Property (Coating Film Consumption Amount (PolishingSpeed) Test)

A test plate having the antifouling coating film was obtained byapplying the obtained antifouling paint to a blast plate, to which arustproof paint had been applied in advance so that a dry film thicknessof a coating film is 300 μm and leaving the blast plate in a room for 2days and nights for drying. This test plate was bonded to a side surfaceof a cylinder having a diameter of 750 mm and a length of 1200 mm, thecylinder was continuously turned for 24 months at a peripheral speed of15 knots, and an amount of consumption of the coating film on the testplate (a total amount of decrease in thickness of the coating film [μm])was measured every three months.

TABLE 14 Reference Example 1 2 3 4 5 6 7 8 9 10 11 Long-Term 3 Months 00 0 0 0 0 0 0 0 0 0 Antifouling 6 Months 0 0 0 0 0 0 0 0 0 0 0 Property12 Months 5 0 0 0 0 0 0 0 0 0 0 [Organism 18 Months 10 0 5 5 0 0 0 5 0 00 Adhesion 24 Months 15 10 10 10 10 10 10 10 10 10 10 Area (%)]Adhesiveness Test 10 10 10 10 10 10 10 10 10 10 10 with Underlying PlateA Substrate Test 10 10 10 10 10 10 10 10 10 10 10 (Cross-Cut Plate BAdhesion Test) Resistance to Immersion A A A A A A A A A A A Cracking inSeawater Repeated A A A A A A A A A A A Drying and Wetting Polishing 3Months 13 15 14 31 35 17 27 42 51 19 19 Property 6 Months 33 29 32 54 7040 55 77 99 36 38 [Amount of 9 Months 48 41 51 73 104 61 74 108 140 5256 Consumption of 12 Months 67 59 70 96 133 82 96 136 175 68 77 CoatingFilm 15 Months 85 72 89 121 161 103 121 161 216 83 96 (μm)] 18 Months104 89 105 144 192 126 144 191 252 100 116 21 Months 127 105 123 170 220149 169 217 291 118 139 24 Months 145 121 142 193 249 172 192 250 — 135160 Reference Example 12 13 14 15 16 17 18 19 Long-Term 3 Months 0 0 0 00 0 0 0 Antifouling 6 Months 0 0 0 0 0 0 0 0 Property 12 Months 0 0 0 00 0 0 0 [Organism 18 Months 5 0 0 5 0 0 0 0 Adhesion 24 Months 10 0 0 100 0 0 0 Area (%)] Adhesiveness Test 10 10 10 10 10 10 10 10 withUnderlying Plate A Substrate Test 10 10 10 10 10 10 101 0 (Cross-CutPlate B Adhesion Test) Resistance to Immersion A A A A A A A A Crackingin Seawater Repeated A A A A A A A A Drying and Wetting Polishing 3Months 44 17 50 11 22 42 11 17 Property 6 Months 77 33 99 22 46 73 26 34[Amount of 9 Months 109 45 150 33 68 104 40 46 Consumption of 12 Months143 58 191 42 86 136 53 59 Coating Film 15 Months 179 73 242 54 110 17067 74 (μm)] 18 Months 211 87 293 67 134 200 82 88 21 Months 248 100 — 80159 236 97 102 24 Months 281 115 — 92 179 267 112 117

TABLE 15 Reference Example 20 21 22 23 24 25 26 27 28 29 30 Long-Term 3Months 0 0 0 0 0 0 0 0 0 0 0 Antifouling 6 Months 0 0 0 0 0 0 0 0 0 0 0Property 12 Months 0 0 0 0 0 0 0 0 0 0 0 [Organism 18 Months 10 0 0 0 00 0 0 0 10 0 Adhesion 24 Months 15 5 0 0 0 0 0 0 0 15 5 Area (%)]Adhesiveness Test 10 10 10 10 10 10 10 10 10 10 10 with Underlying PlateA Substrate Test 10 10 10 10 10 10 10 10 10 10 10 (Cross-Cut Plate BAdhesion Test) Resistance to Immersion A A A A A A A A A A A Cracking inSeawater Repeated A A A A A A A A A A A Drying and Wetting Polishing 3Months 12 13 43 23 18 21 30 29 30 19 18 Property 6 Months 27 35 85 45 3239 55 56 59 39 42 [Amount of 9 Months 43 54 127 67 45 57 79 83 86 57 61Consumption of 12 Months 58 71 171 90 61 80 106 112 114 75 79 CoatingFilm 15 Months 71 89 212 114 79 98 132 139 142 94 99 (μm)] 18 Months 85108 251 141 98 122 154 162 172 114 119 21 Months 101 126 292 165 117 143179 185 200 136 138 24 Months 116 145 — 188 133 164 204 213 228 153 158Reference Example 31 32 33 34 35 36 37 38 Long-Term 3 Months 0 0 0 0 0 00 0 Antifouling 6 Months 0 0 0 0 0 0 0 0 Property 12 Months 0 0 0 0 0 00 0 [Organism 18 Months 0 0 0 0 0 0 0 0 Adhesion 24 Months 0 0 0 0 0 0 00 Area (%)] Adhesiveness Test 10 10 10 10 10 10 10 10 with UnderlyingPlate A Substrate Test 10 10 10 10 10 10 10 10 (Cross-Cut Plate BAdhesion Test) Resistance to Immersion A A A A A A A A Cracking inSeawater Repeated A A A A A A A A Drying and Wetting Polishing 3 Months21 14 37 16 16 15 40 14 Property 6 Months 38 24 69 30 37 30 79 24[Amount of 9 Months 57 34 102 43 53 46 118 34 Consumption of 12 Months78 46 137 58 69 61 158 47 Coating Film 15 Months 97 59 170 73 85 75 19960 (μm)] 18 Months 117 73 198 89 103 92 240 74 21 Months 139 86 230 103121 107 281 88 24 Months 158 100 262 118 138 122 — 102

TABLE 16 Reference Example 39 40 41 42 43 44 45 46 47 48 49 50 Long-Term3 Months 0 0 0 0 0 0 0 0 0 0 0 0 Antifouling 6 Months 0 0 0 0 0 0 0 0 00 0 0 Property 12 Months 0 0 0 0 0 0 0 0 0 0 0 0 [Organism 18 Months 0 00 0 0 0 0 0 0 0 0 0 Adhesion 24 Months 0 0 0 0 0 0 0 0 0 0 0 0 Area (%)]Adhesiveness Test 10 10 10 10 10 10 10 10 10 10 10 10 with UnderlyingPlate A Substrate Test 10 10 10 10 10 10 10 10 10 10 10 10 (Cross-CutPlate B Adhesion Test) Resistance to Immersion A A A A A A A A A A A ACracking in Seawater Repeated A A A A A A A A A A A A Drying and WettingPolishing 3 Months 22 23 28 15 15 13 14 18 17 14 17 17 Property 6 Months47 41 51 39 33 29 32 39 42 30 37 36 [Amount of 9 Months 65 63 79 61 5146 51 59 68 46 58 55 Consumption of 12 Months 82 85 106 79 68 63 69 7988 61 77 73 Coating Film 15 Months 103 106 133 99 86 80 88 100 111 77 9792 (μm)] 18 Months 120 125 156 115 103 95 105 121 129 93 117 112 21Months 138 144 180 134 121 109 120 142 150 109 137 131 24 Months 154 164205 150 139 124 136 164 169 125 158 150 Reference Example 51 52 53 54 5556 57 58 59 Long-Term 3 Months 0 0 0 0 0 0 0 0 0 Antifouling 6 Months 00 0 0 0 0 0 0 0 Property 12 Months 0 0 0 0 0 0 0 0 0 [Organism 18 Months0 0 0 0 0 0 0 0 0 Adhesion 24 Months 0 0 0 0 0 0 0 0 0 Area (%)]Adhesiveness Test 10 10 10 10 10 10 10 10 10 with Underlying Plate ASubstrate Test 10 10 10 10 10 10 10 10 10 (Cross-Cut Plate B AdhesionTest) Resistance to Immersion A A A A A A A A A Cracking in SeawaterRepeated A A A A A A A A A Drying and Wetting Polishing 3 Months 23 1014 14 16 24 13 15 21 Property 6 Months 50 25 36 30 36 43 28 33 45[Amount of 9 Months 77 40 55 48 56 66 42 51 62 Consumption of 12 Months102 51 72 66 75 90 56 68 78 Coating Film 15 Months 129 64 90 84 94 11371 86 98 (μm)] 18 Months 154 75 105 100 113 133 86 104 114 21 Months 18287 122 114 133 154 100 122 131 24 Months 209 98 137 130 153 174 115 140146

TABLE 17 Comparative Reference Example 1 2 3 4 5 6 7 Long-Term 3 Months60 10 0 40 30 0 0 Antifouling 6 Months 100 40 30 80 70 0 10 Property 12Months 100 80 70 100 90 50 30 [Organism 18 Months 100 100 100 100 100 8050 Adhesion 24 Months 100 100 100 100 100 100 70 Area (%)] AdhesivenessTest 0 10 10 8 4 8 10 with Underlying Plate A Substrate Test 0 10 10 8 48 10 (Cross-Cut Plate B Adhesion Test) Resistance to Immersion B A A B AB A Cracking in Seawater Repeated 10 A A 16 A 16 A Drying and WettingPolishing 3 Months 0 19 82 32 8 20 19 Property 6 Months 0 35 99 57 20 4535 [Amount of 9 Months 0 51 111 79 31 67 51 Consumption of 12 Months 071 124 101 40 89 71 Coating Film 15 Months 0 89 127 127 50 115 89 (μm)]18 Months 0 107 129 168 58 156 107 21 Months 0 127 134 222 67 210 127 24Months 0 144 137 272 75 260 144

As shown in Tables 14 to 17, the antifouling coating film obtained fromthe antifouling paint in the reference example containing hydrolyzableresin (i) or (ii) is excellent in a long-term antifouling property,adhesiveness with an underlying substrate, and resistance to cracking.On the other hand, the antifouling coating film obtained from theantifouling paint in the comparative reference example was notsufficient in a long-term antifouling property, and some were poor inresistance to cracking or adhesiveness with an underlying substrate.

1. A method of forming an antifouling coating film on a surface of anobject to be coated, comprising the steps of: [1] preparing a coloredantifouling paint containing a hydrolyzable resin and a color pigmentand satisfying such conditions that (a) a coating film formed from saidcolored antifouling paint having a target dry film thickness Tcompletely hides the surface of said object to be coated, (b) a colordifference ΔE1 between the coating film formed from said coloredantifouling paint having the target dry film thickness T and a coatingfilm formed from said colored antifouling paint having a dry filmthickness of 0.8 T is equal to or greater than 2.0, and (c) saidhydrolyzable resin contains a hydrolyzable resin (i) and/or ahydrolyzable resin (ii); and [2] coating the surface of said object tobe coated with said colored antifouling paint until the surface of saidobject to be coated is completely hidden by the coating film formed fromsaid colored antifouling paint, said hydrolyzable resin (i) being ahydrolyzable resin having a metal-atom-containing group containing adivalent metal atom M and at least one type of a silicon-containinggroup selected from the group consisting of a group expressed in ageneral formula (I)

[where a and b each independently represent an integer from 2 to 5, mrepresents an integer from 0 to 50, n represents an integer from 3 to80, and R¹ to R⁵ each independently represent an alkyl group, an alkoxygroup, a phenyl group, a substituted phenyl group, a phenoxy group, or asubstituted phenoxy group], a group expressed in a general formula (II)

[where c and d each independently represent an integer from 2 to 5, prepresents an integer from 0 to 50, and R⁶, R⁷, and R⁸ eachindependently represent an alkyl group, R^(a), or R^(b), with R^(a)being

(where x represents an integer from 0 to 20 and R²³ to R²⁷ are identicalor different and represent an alkyl group), with R^(b) being

(where y represents an integer from 1 to 20 and R²⁸ and R²⁹ areidentical or different and represent an alkyl group)], a group expressedin a general formula (III)

[where e, f, g, and h each independently represent an integer from 2 to5, q and s each independently represent an integer from 0 to 50, rrepresents an integer from 3 to 80, and R⁹ to R¹² each independentlyrepresent an alkyl group, an alkoxy group, a phenyl group, a substitutedphenyl group, a phenoxy group, or a substituted phenoxy group], and agroup expressed in a general formula (IV)

[where i, j, k, and l each independently represent an integer from 2 to5, t and u each independently represent an integer from 0 to 50, v and weach independently represent an integer from 0 to 20, and R¹³ to R²² areidentical or different and represent an alkyl group], and saidhydrolyzable resin (ii) being a hydrolyzable resin having at least onetype of silicon-containing group selected from the group consisting ofthe groups expressed in said general formulae (I), (II), (III), and (IV)and a triorganosilyloxy carbonyl group expressed in a general formula(V)

[where R⁴⁰, R⁴¹, and R⁴² are identical or different and represent ahydrocarbon residue having a carbon number from 1 to 20].
 2. The methodof forming an antifouling coating film according to claim 1, whereinsaid color difference ΔE1 is not smaller than 2.5.
 3. The method offorming an antifouling coating film according to claim 1, wherein saidcolored antifouling paint satisfies such a condition (d) that a colordifference ΔE2 between the coating film formed from said coloredantifouling paint having the target dry film thickness T and a coatingfilm formed from said colored antifouling paint having a dry filmthickness of 1.2 T is less than
 1. 4. The method of forming anantifouling coating film according to claim 3, wherein said colordifference ΔE2 is not greater than 0.5.
 5. The method of forming anantifouling coating film according to claim 1, wherein saidmetal-atom-containing group which said hydrolyzable resin (i) has is atleast one type of group selected from the group consisting of groupsexpressed in general formulae (VI) and (VII)

[where M represents a divalent metal atom and R³⁰ represents an organicacid residue or an alcohol residue]

[where M represents a divalent metal atom].
 6. The method of forming anantifouling coating film according to claim 1, wherein said hydrolyzableresin (i) includes a constitutional unit derived from at least one typeof a silicon-containing polymerizable monomer (a) selected from thegroup consisting of a monomer (a1) expressed in a general formula (I′)below, a monomer (a2) expressed in a general formula (II′) below, amonomer (a3) expressed in a general formula (III′) below, and a monomer(a4) expressed in a general formula (IV′) below and a constitutionalunit derived from a metal-atom-containing polymerizable monomer (b)containing a divalent metal atom M

[where R³¹ represents a hydrogen atom or a methyl group, and a, b, m, n,and R¹ to R⁵ represent meaning as described previously]

[where R³² represents a hydrogen atom or a methyl group, and c, d, p,and R⁶ to R⁸ represent meaning as described previously]

[where R³³ and R³⁴ represent a hydrogen atom or a methyl group, and e,f, g, h, q, r, s, and R⁹ to R¹² represent meaning as describedpreviously]

[where R³⁵ and R³⁶ represent a hydrogen atom or a methyl group, and i,j, k, l, t, u, v, w, and R¹³ to R²² represent meaning as describedpreviously].
 7. The method of forming an antifouling coating filmaccording to claim 6, wherein said metal-atom-containing polymerizablemonomer (b) includes at least one type selected from the groupconsisting of a monomer (b1) expressed in a general formula (VP) belowand a monomer (b2) expressed in a general formula (VIP) below

[where R³⁷ represents a hydrogen atom or a methyl group and M and R³⁰represent meaning as described previously]

[where R³⁸ and R³⁹ represent a hydrogen atom or a methyl group and Mrepresents meaning as described previously].
 8. The method of forming anantifouling coating film according to claim 1, wherein said hydrolyzableresin (ii) further has at least one type of metal-atom-containing groupselected from the group consisting of groups expressed in generalformulae (VI) and (VII)

[where M represents a divalent metal atom and R³⁰ represents an organicacid residue or an alcohol residue]

[where M represents a divalent metal atom].
 9. The method of forming anantifouling coating film according to claim 1, wherein said hydrolyzableresin (ii) includes a constitutional unit derived from at least one typeof a silicon-containing polymerizable monomer (a) selected from thegroup consisting of a monomer (a1) expressed in a general formula (I′)below, a monomer (a2) expressed in a general formula (II′) below, amonomer (a3) expressed in a general formula (III′) below, and a monomer(a4) expressed in a general formula (IV′) below and a constitutionalunit derived from triorganosilyl(meth)acrylate (c) expressed in ageneral formula (V′) below

[where R³¹ represents a hydrogen atom or a methyl group, and a, b, m, n,and R¹ to R⁵ represent meaning as described previously]

[where R³² represents a hydrogen atom or a methyl group, and c, d, p,and R⁶ to R⁸ represent meaning as described previously]

[where R³³ and R³⁴ represent a hydrogen atom or a methyl group, and e,f, g, h, q, r, s, and R⁹ to R¹² represent meaning as describedpreviously]

[where R³⁵ and R³⁶ represent a hydrogen atom or a methyl group, and i,j, k, l, t, u, v, w, and R¹³ to R²² represent meaning as describedpreviously]

[where R⁴³ represents a hydrogen atom or a methyl group and R⁴⁰ to R⁴²represent meaning as described previously].
 10. The method of forming anantifouling coating film according to claim 9, wherein said hydrolyzableresin (ii) further includes a constitutional unit derived from at leastone type of a metal-atom-containing polymerizable monomer (b) selectedfrom the group consisting of a monomer (b1) expressed in a generalformula (VI′) below and a monomer (b2) expressed in a general formula(VII′) below

[where R³⁷ represents a hydrogen atom or a methyl group and M and R³⁰represent meaning as described previously]

[where R³⁸ and R³⁹ represent a hydrogen atom or a methyl group and Mrepresents meaning as described previously].
 11. The method of formingan antifouling coating film according to claim 1, wherein said coloredantifouling paint further contains an antifouling agent, and a contentof said antifouling agent is equal to or lower than 10 mass % in a paintsolid content.
 12. The method of forming an antifouling coating filmaccording to claim 1, wherein said colored antifouling paint furthercontains a thermoplastic resin and/or a plasticizer, and a total contentof said thermoplastic resin and said plasticizer is 3 to 100 parts bymass with respect to 100 parts by mass of said hydrolyzable resin. 13.The method of forming an antifouling coating film according to claim 1,wherein said colored antifouling paint is prepared by mixing two or moretypes of antifouling paints satisfying said conditions (a) to (c), andsaid two or more types of antifouling paints are different from oneanother in content of the color pigment.
 14. The method of forming anantifouling coating film according to claim 1, wherein said object to becoated has an undercoat coating film formed from an anti-corrosive paintor an antifouling paint on its surface, and a surface of said undercoatcoating film is coated with said colored antifouling paint.
 15. Themethod of forming an antifouling coating film according to claim 1,wherein said object to be coated is made of steel, plastic, or concrete.